Water-based metal-containing organic phosphate compositions

ABSTRACT

Water-based metal-containing organic phosphate compositions which are useful as corrosion-inhibiting coating compositions, metal working lubricants and drilling fluids for well-drilling operations are disclosed. These compositions comprise: (A) water or an aqueous drilling mud; (B) an overbased non-Newtonian colloidal disperse system comprising (B)(1) solid metal-containing colloidal particles predispersed in (B)(2) a dispersing medium of at least one inert organic liquid and (B)(3) at least one member selected from the class consisting of organic compounds which are substantially soluble in said dispersing medium, the molecules of said organic compound being characterized by polar substituents and hydrophobic portions; and (C) a metal-containing organic phosphate complex derived from the reaction of (C)(1) at least one polyvalent metal salt of an acid phosphate ester, said acid phosphate ester being derived from the reaction of phosphorus pentoxide or phosphoric acid with a mixture of at least one monohydric alcohol and at least one polyhydric alcohol, with (C)(2) at least one organic epoxide. These compositions preferably include an effective amount of (D) an alkali or an alkaline earth metal salt of an organic acid, (E) a carboxylic acid and (F) an N-(hydroxyl-substituted hydrocarbyl) amine to enhance the dispersion of components (B) and (C) with said water or drilling mud (A).

TECHNICAL FIELD

This invention relates to water-based metal-containing organic phosphatecompositions which are useful as corrosion-inhibiting coatings, metalworking lubricants and drilling fluids for well-drilling operations.These compositions comprise water, an overbased non-Newtonian colloidaldisperse system and a metal-containing organic phosphate complex. Thesecompositions also preferably contain an effective amount of at least onealkali or alkaline earth metal salt of an organic acid, at least onecarboxylic acid and at least one N-(hydroxyl-substitutedhydrocarbyl)amine to enhance the dispersion of the non-Newtoniancolloidal disperse system and metal-containing organic phosphate complexwith the water.

BACKGROUND OF THE INVENTION

The corrosion of metal articles is of obvious economic significance inany industrial application and, as a consequence, the inhibition of suchcorrosion is a matter of prime consideration. It is particularlysignificant to users of steel and other ferrous alloys. The corrosion ofsuch ferrous metal alloys is largely a matter of rust formation, whichin turn involves the overall conversion of the free metal to its oxides.

The theory which best explains such oxidation of ferrous metal articlespostulates the essential presence of both water and oxygen. Even minutetraces of moisture are sufficient, according to this theory, to inducedissolution of iron therein and the formation of ferrous hydroxide untilthe water becomes saturatd with ferrous ions. The presence of oxygencauses oxidation of the resulting ferrous hydroxide to ferric hydroxide,which settles out of solution and is ultimately converted to ferricoxide or rust.

The above sequence of reactions can be prevented, or at least in largemeasure inhibited, by relatively impermeable coatings which have theeffect of excluding moisture and/or oxygen from contact with the metalsurface. It is important, therefore, that these coatings adhere tightlyto the metal surface and resist flaking, crazing, blistering, powdering,and other forms of loss of adhesion. A satisfactory corrosion-proofingcoating, therefore, must have the ability to resist weathering, highhummidity, and corrosive atmospheres such as salt-laden mist or fog, aircontaminated with industrial waste, etc., so that a uniform protectivefilm is maintained on all or most of the metal surface.

U.S. Pat. Nos. 3,215,715 and 3,276,916 disclose metal-containingphosphate complexes for inhibiting the corrosion of metal. Thesecomplexes are prepared by the reaction of (A) a polyvalent metal salt ofthe acid phosphate esters derived from the reaction of phosphoruspentoxide with a mixture of a monohydric alcohol and from 0.25 to 4.0equivalents of a polyhydric alcohol, with (B) at least about 0.1equivalent of an organic epoxide.

U.S. Pat. No. 3,411,923 discloses metal-containing organic phosphatecompositions for inhibiting the corrosion of metals which comprise (A) ametal-containing organic phosphate complex prepared by the process whichcomprises the reaction of (I) a polyvalent metal salt of an acidphosphate ester derived from the reaction of phosphorus pentoxide orphosphoric acid with a mixture of a monohydric alcohol and from about0.25 to about 4.0 equivalents of a polyhydric alcohol with (II) at leastabout 0.1 equivalent of an organic epoxide, and (B) a basic alkali oralkaline earth metal salt of a sulfonic or carboxylic acid having atleast about 12 aliphatic carbon atoms, said salt having a metal ratio ofat least about 1.1.

The foregoing corrosion-inhibiting compositions are oil-basedcompositions. That is, they are usually diluted with mineral oil orvolatile diluents such as benzene, xylene, aromatic petroleum spirits,turpentine, etc. It would be advantageous to replace these oil-basedcompositions with water-based compositions wherever possible.

Metal working operations, for example, rolling, forging, hot-pressing,blanking, bending, stamping, drawing, cutting, punching, spinning andthe like generally employ a lubricant to facilitate the same. Lubricantsgreatly improve these operations in that they can reduce the powerrequired for the operation, prevent sticking and decrease wear of dies,cutting bits and the like. In addition, they frequently provide rustinhibiting properties to the metal being treated. These lubricants areusualy oil-based and it would be advantageous to replace such oil-basedlubricants with water-based lubricants wherever possible.

The use of drilling fluids in well-drilling operations has been knownfor at least 100 years. See, for example, the discussion in Kirk-Othmer."Encyclopedia of Chemical Technology", Second Edition, Vol. 7, pages 287et seq. Aqueous drilling fluids or muds usually contain a thickeningagent such as clay and often a density-increasing agent such as barites.The use of other additives in drilling fluids or muds is also known.See, for example, John McDermott, "Drilling Mud and Fluid Additives",Noyes-Data Corporation, New Jersey, 1973.

Among the types of additives used in drilling muds or fluids arelubricants or lubricity agents. Such additives reduce drag on the drillstring and bit and thereby reduce the possibilities of twist off, reducetrip time, lessen differential sticking and lower the amount of energyrequired to turn the rig (that is, the torque requirements). Methods forevaluating such drilling fluid lubricants are also known. See, forexample, the article by Stan E. Alford in "World Oil", July, 1976, GulfPublishing Company.

Other additives which enhance the lubricating properties of drillingfluids or muds have been reported in the patent literature. See, forexample, U.S. Pat. Nos. 3,214,374 and 4,064,055. The use of petroleumsulfonates as extreme pressure additives in oil emulsion and aqueousdrilling fluids is also known. See the articcle by M. Rosenberg et al inAIME Petroleum Transactions, Vol. 216 (1959), pages 195-202 and U.S.Pat. No. 4,064,056.

U.S. Pat. No. 4,230,586 discloses aqueous well-drilling fluids whichcomprise (A) at least one non-Newtonian colloidal disperse systemcomprising:

(1) solid metal-containing colloidal particles at least a portion ofwhich are predispersed in

(2) at least one liquid dispersing medium; and

(3) as an essential component, at least one organic compound which issoluble in said dispersing medium, the molecules of said organiccompound being characterized by a hydrophobic portion and at least onepolar substituent

and (B) at least one emulsifier.

Despite the foregoing, the search for effective drilling fluids, whichaid in achieving more efficient and economical rotary drillingoperations, has continued.

SUMMARY OF THE INVENTION

The present invention contemplates the provision of water-basedmetal-containing organic phosphate compositions which are useful ascorrosion-inhibiting coating compositions, metal working lubricants anddrilling fluids for well-drilling operations.

Broadly stated, the present invention provides for a compositioncomprising: (A) water; (B) an overbased non-Newtonian colloidal dispersesystem comprising (B)(1) solid metal-containing colloidal particlespredispersed in (B)(2) a dispersing medium of at least one inert organicliquid and (B)(3) at least one member selected from the class consistingof organic compounds which are substantially soluble in said dispersingmedium, the molecules of said organic compound being characterized bypolar substituents and hydrophobic portions; and (C) a metal-containingorganic phosphate complex derived from the reaction of (C)(1) at leastone polyvalent metal salt of an acid phosphate ester, said acidphosphate ester being derived from the reaction of phosphorus pentoxideor phosphoric acid with a mixture of at least one monohydric alcohol andat least one polyhydric alcohol, with (C)(2) at least one organicepoxide; components (B) and (C) being dispersed with said water.

In a preferred embodiment, the present invention provides for a drillingfluid comprising (A) a major amount of an aqueous drilling mud, and aminor torque reducing amount of a mixture of: (B) an overbasednon-Newtonian colloidal disperse system comprising (B)(1) solidmetal-containing colloidal particles predispersed in (B)(2) a dispersingmedium of at least one inert organic liquid and (B)(3) at least onemember selected from the class consisting of organic compounds which aresubstantially soluble in said dispersing medium, the molecules of saidorganic compound being characterized by polar substituents andhydrophobic portions; and (C) a metal-containing organic phosphatecomplex derived from the reaction of (C)(1) at least one polyvalentmetal salt of an acid phosphate ester, said acid phosphate ester beingderived from the reaction of phosphorus pentoxide or phosphoric acidwith a mixture of a monohydric alcohol and a polyhydric alcohol, with(C)(2) at least one organic epoxide.

The foregoing compositions and drilling fluids preferably include aneffective amount of (D) an alkali or an alkaline earth metal salt of anorganic acid, (E) a carboxylic acid and (F) an N-(hydroxyl-substitutedhydrocarbyl)amine to enhance the dispersion of components (B) and (C)with said water or drilling mud (A).

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The Water or DillingMud (A)

When the compositions of the present invention are to be employed ascorrosion-inhibiting coating compositions or metal working lubricants,component (A) is water.

When the compositions of the present invention are in the form of adrilling fluid, component (A) is an aqueous drilling mud. These drillingmuds are usually suspensions of solids in water; these solids form thebulk of the mud filter cake. In general, the solids are clay and bariteand their relative amounts present in the bulk mud are controlled withinlimits set by the required mud density. The drilling muds contemplatedherein are entirely conventional and well known to those skilled in theart. Reference is made to John McDermott, "Drilling Mud and FluidAdditives", Noyes-Data Corporation, New Jersey, 1973, which isincorporated herein by reference.

The Overbased Non-Newtonian Disperse System (B)

The terminology "disperse system" as used in the specification andclaims is a term of art generic to colloids or colloidal solutions,e.g., "any homogeneous medium containing dispersed entities of any sizeand state", Jirgensons and Straumanis, "A Short Textbook on ColloidalChemistry" (2nd Ed.) The MacMillan Co., New York, 1962 at page 1.However, the particular disperse systems of the present invention form asubgenus within this broad class of disperse system, this subgenus beingcharacterized by several important features.

So long as the solid particles remain dispersed in the dispersing mediumas colloidal particles the particle size is not critical. Ordinarily,the particles will not exceed 5000 A. However, it is preferred that themaximum unit particle size be less than about 1000 A. In a particularlypreferred aspect of the invention, the unit particle size is less thanabout 400 A. Systems having a unit particle size in the range of 30 A to200 A are useful. The minimum unit particle size is at least 20 A andpreferably at least about 30 A.

The language "unit particle size" is intended to designate the averageparticle size of the solid, metal-containing particles assuming maximumdispersion of the individual particles throughout the disperse medium.That is, the unit particle is that particle which corresponds in size tothe average size of the metal-containing particles and is capable ofindependent existence within the disperse system as a discrete colloidalparticle. These metal-containing particles are found in two forms in thedisperse systems. Individual unit particles can be dispersed as suchthroughout the medium or unit particles can form an agglomerate, incombination with other materials (e.g., another metal-containingparticle, the disperse medium, etc.) which are present in the dispersesystems. These agglomerates are dispersed through the system as"metal-containing particles". Obviously, the "particle size" of theagglomerate is substantially greater than the unit particle size.Furthermore, it is equally apparent that this agglomerate size issubject to wide variations, even within the same disperse system. Theagglomerate size varies, for example, with the degree of shearing actionemployed in dispersing the unit particles. That is, mechanical agitationof the disperse system tends to break down the agglomerates into theindividual components thereof and disperse these individual componentsthroughout the disperse medium. The ultimate in dispersion is achievedwhen each solid, metal-containing particle is individually dispersed inthe medium. Accordingly, the disperse systems are characterized withreference to the unit particle size, it being apparent to those skilledin the art that the unit particle size represents the average size ofsolid, metal-containing particles present in the system which can existindependently. The average particle size of the metal-containing solidparticles in the system can be made to approach the unit particle sizevalue by the application of a shearing action to the existent system orduring the formation of the disperse system as the particles are beingformed in situ. It is not necessary that maximum particle dispersionexist to have useful disperse systems. The agitation associated withhomogenization of the overbased material and conversion agent producessufficient particle dispersion.

Basically, the solid metal-containing particles are in the form of metalsalts of inorganic acids, and low molecular weight organic acids,hydrates thereof, or mixtures of these. These salts are usually thealkali and alkaline earth metal formates, acetates, carbonates, hydrogencarbonates, hydrogen sulfides, sulfites, hydrogen sulfites, and halides,particularly chlorides. In other words, the metal-containing particlesare ordinarily particles of metal salts, the unit particle is theindividual salt particle and the unit particle size is the averageparticle size of the salt particles which is readily ascertained, as forexample, by conventional X-ray diffraction techniques. Colloidaldisperse systems possessing particles of this type are sometimesreferred to as macromolecular colloidal systems.

Because of the composition of the colloidal disperse systems of thisinvention, the metal containing particles also exist as components inmicellar colloidal particles. In addition to the solid metal-containingparticles and the disperse medium, the colloidal disperse systems of theinvention are characterized by a third essential component, one which issoluble in the medium and contains in the molecules thereof ahydrophobic portion and at least one polar substituent. This thirdcomponent can orient itself along the external surfaces of the abovemetal salts, the polar groups lying along the surface of these saltswith the hydrophobic portions extending from the salts into the dispersemedium forming micellar colloidal particles. These micellar colloids areformed through weak intermolecular forces, e.g., Van der Waals forces,etc. Micellar colloids represent a type of agglomerate particle asdiscussed hereinabove. Because of the molecular orientation in thesemicellar colloidal particles, such particles are characterized by ametal-containing layer (i.e., the solid metal-containing particles andany metal present in the polar substituent of the third component, suchas the metal in a sulfonic or carboxylic acid salt group), a hydrophobiclayer formed by the hydrophobic portions of the molecules of the thirdcomponent and a polar layer bridging said metal-containing layer andsaid hydrophobic layer, said polar bridging layer comprising the polarsubstituents of the third component of the system, e.g., the ##STR1##group if the third component is an alkaline earth metal petrosulfonate.

The second essential component of the colloidal disperse system is thedispersing medium. The identity of the medium is not a particularlycritical aspect of the invention as the medium primarily serves as theliquid vehicle in which solid particles are dispersed. The medium canhave components characterized by relatively low boiling points, e.g., inthe range of 25° C. to 120° C. to facilitate subsequent removal of aportion or substantially all of the medium from the aqueous compositionsor drilling fluids of the invention or the components can have a higherboiling point to protect against removal from such compositions ordrilling fluids upon standing or heating. There is no criticality in anupper boiling point limitation on these liquids.

Representative liquids include mineral oils, the alkanes and haloalkanesof 5 to 18 carbon atoms, polyhalo- and perhaloalkanes of up to about 6carbons, the cycloalkanes of 5 or more carbons, the corresponding alkyl-and/or halo-substituted cycloalkanes, the aryl hydrocarbons, thealkylaryl hydrocarbons, the haloaryl hydrocarbons, ethers such asdialkyl ethers, alkyl aryl ethers, cycloalkyl ethers, cycloalkylalkylethers, alkanols, alkylene glycols, polyalkylene glycols, alkyl ethersof alkylene glycols and polyalkylene glycols, dibasic alkanoic aciddiesters, silicate esters, and mixtures of these. Specific examplesinclude petroleum ether, Stoddard Solvent, pentane, hexane, octane,isooctane, undecane, tetradecane, cyclopentane, cyclohexane,isopropylcyclohexane, 1,4-dimethylcyclohexane, cyclooctane, benzene,toluene, xylene, ethyl benzene, tert-butylbenzene, halobenzenesespecially mono- and polychlorobenzenes such as chlorobenzene per se and3,4-dichlorotoluene, mineral oils, n-propylether, isopropylether,isobutylether, n-amylether, methyl-n-amylether, cyclohexylether,ethoxycyclohexane, methoxybenzene, isopropoxy benzene,p-methoxy-toluene, methanol, ethanol, propanol, isopropanol, hexanol,n-octyl alcohol, n-decyl alcohol, alkylene glycols such as ethyleneglycol and propylene glycol, diethyl ketone, dipropyl ketone,methylbutyl ketone, acetophenone, 1,2-difluoro tetrachloroethane,dichlorofluoromethane, 1,2-dibromotetrafluoroethane,trichlorofluoromethane, 1-chloropentane, 1,3-dichlorohexane, formamide,dimethylformamide, acetamide, dimethylacetamide, diethylacetamide,propionamide, diisooctyl azelate, ethylene glycol, polypropyleneglycols, hexa-2-ethylbutoxy disiloxane, etc.

Also useful as dispersing medium are the low molecular weight, liquidpolymers, generally classified as oligomers, which include the dimers,tetramers, pentamers, etc. Illustrative of this large class of materialsare such liquids as the propylene tetramers, isobutylene dimers, and thelike.

From the standpoint of availability, cost, and performance, the alkyl,cycloalkyl, and aryl hydrocarbons represent a preferred class ofdisperse mediums. Liquid petroleum fractions represent another preferredclass of disperse mediums. Included within these preferred classes arebenzenes and alkylated benzenes, cycloalkanes and alkylatedcycloalkanes, cycloalkenes and alkylated cycloalkenes such as found innaphthene-based petroleum fractions, and the alkanes such as found inthe paraffin-based petroleum fractions. Petroleum ether, naphthas,mineral oils, Stoddard Solvent, toluene, xylene, etc., and mixturesthereof are examples of economical sources of suitable inert organicliquids which can function as the disperse medium in the colloidaldisperse systems of the present invention. Mineral oil can serve byitself as the disperse medium.

Preferred disperse systems include those containing at least somemineral oil as a component of the disperse medium. Any amount of mineraloil is beneficial in this respect. However, in this preferred class ofsystems, it is desirable that mineral oil comprise at least about 1% byweight of the total medium, and preferably at least about 5% by weight.Those mediums comprising at least 10% by weight mineral oil areespecially useful. Mineral oil can serve as the exclusive dispersemedium.

In addition to the solid, metal-containing particles and the dispersemedium, the disperse systems employed herein require a third essentialcomponent. This third component is an organic compound which is solublein the disperse medium, and the molecules of which are characterized bya hydrophobic portion and at least one polar substituent. As explained,infra, the organic compounds suitable as a third component are extremelydiverse. These compounds are inherent constituents of the dispersesystems as a result of the methods used in preparing the systems.Further characteristics of the components are apparent from thefollowing discussion of methods for preparing the colloidal dispersesystems.

Preparation of the Overbased Non-Newtonian Disperse System (B)

Broadly speaking, the colloidal disperse systems of the invention areprepared by treating a single phase homogeneous, Newtonian system of an"overbased", "superbased", or "hyperbased", organic compound with aconversion agent, usually an active hydrogen containing compound, thetreating operation being simply a thorough mixing together of the twocomponents, i.e., homogenization. This treatment converts these singlephase systems into the non-Newtonian colloidal disperse systems utilizedin the compositions of the present invention.

The terms "overbased", "superbased", and "hyperbased", are terms of artwhich are generic to well known classes of metal-containing materials.These overbased materials have also been referred to as "complexes","metal complexes", "high-metal containing salts", and the like.Overbased materials are characterized by a metal content in excess ofthat which would be present according to the stoichiometry of the metaland the particular organic compound reacted with the metal, e.g., acarboxylic or sulfonic acid. Thus, if a monosulfonic acid, ##STR2## isneutralized with a basic metal compound, e.g., calcium hydroxide, the"normal" metal salt produced will contain one equivalent of calcium foreach equivalent of acid, i.e., ##STR3## However, as is well known in theart, various processes are available which result in an inert organicliquid solution of a product containing more than the stoichiometricamount of metal. The solutions of these products are referred to hereinas overbased materials. Following these procedures, the sulfonic acid oran alkali or alkaline earth metal salt thereof can be reacted with ametal base and the product will contain an amount of metal in excess ofthat necessary to neutralize the acid, for example, 4.5 times as muchmetal as present in the normal salt or a metal excess of 3.5equivalents. The actual stoichiometric excess of metal can varyconsiderably, for example, from about 0.1 equivalent to about 30 or moreequivalents depending on the reactions, the process conditions, and thelike. These overbased materials useful in preparing the disperse systemsusually contain from about 3.5 to about 30 or more equivalents of metalfor each equivalent of material which is overbased.

In the present specification and claims the term "overbased" is used todesignate materials containing a stoichiometric excess of metal and is,therefore, inclusive of those materials which have been referred to inthe art as overbased, superbased, hyperbased, etc., as discussed supra.

The terminology "metal ratio" is used in the prior art and herein todesignate the ratio of the total chemical equivalents of the metal inthe overbased material (e.g., a metal sulfonate or carboxylate) to thechemical equivalents of the metal in the product which would be expectedto result in the reaction between the organic material to be overbased(e.g., sulfonic or carboxylic acid) and the metal-containing reactant(e.g., calcium hydroxide, barium oxide, etc.) according to the knownchemical reactivity and stoichiometry of the two reactants. Thus, in thenormal calcium sulfonate discussed above, the metal ratio is one, and inthe overbased sulfonate, the metal ratio is 4.5. Obviously, if there ispresent in the material to be overbased more than one compound capableof reacting with the metal, the "metal ratio" of the product will dependupon whether the number of equivalents of metal in the overbased productis compared to the number of equivalents expected to be present for agiven single component or a combination of all such components.

The overbased materials are prepared by treating a reaction mixturecomprising the organic material to be overbased, a reaction mediumconsisting essentially of at least one inert, organic solvent for saidorganic material, a stoichiometric excess of a metal base, and apromoter with an acidic material. The methods for preparing theoverbased materials as well as an extremely diverse group of overbasedmaterials are well known in the prior art and are disclosed for examplein the following U.S. Pat. Nos.: 2,616,904; 2,616,905; 2,616,906;2,616,911; 2,616,924; 2,616,925; 2,617,049; 2,695,910; 2,723,234;2,723,235; 2,723,236; 2,760,970; 2,767,164; 2,767,209; 2,777,874;2,798,852; 2,839,470; 2,856,359; 2,859,360; 2,856,361; 2,861,951;2,883,340; 2,915,517; 2,959,551; 2,968,642; 2,971,014; 2,989,463;3,001,981; 3,027,325; 3,070,581; 3,108,960; 3,133,019; 3,146,201;3,147,232; 3,152,991; 3,155,616; 3,170,880; 3,170,881; 3,172,855;3,194,823; 3,223,630; 3,232,883; 3,242,079; 3,242,080; 3,250,710;3,256,186; 3,274,135; 3,492,231; 4,230,586; 4,436,855; and 4,443,577.These patents disclose processes, materials which can be overbased,suitable metal bases, promoters, and acidic materials, as well as avariety of specific overbased products useful in producing the dispersesystems of this invention. These patents are incorporated herein byreference.

An important characteristic of the organic materials which are overbasedis their solubility in the particular reaction medium utilized in theoverbasing process. As the reaction medium used previously has normallycomprised petroleum fractions, particularly mineral oils, these organicmaterials have generally been oil-soluble. However, if another reactionmedium is employed (e.g., aromatic hydrocarbons, aliphatic hydrocarbons,kerosene, etc.) it is not essential that the organic materials besoluble in mineral oil as long as it is soluble in the given reactionmedium. Obviously, many organic materials which are soluble in mineraloils will be soluble in many of the other indicated suitable reactionmediums. It should be apparent that the reaction medium usually becomesthe disperse medium of the colloidal disperse system or at least acomponent thereof depending on whether or not additional inert organicliquid is added as part of the reaction medium or the disperse medium.

Materials which can be overbased are generally oil-soluble organic acidsincluding phosphorus acids, thiophosphorus acids, sulfur acids,carboxylic acids, thiocarboxylic acids, and the like, as well as thecorresponding alkali and alkaline earth metal salts thereof. U.S. Pat.No. 2,777,874 discloses organic acids suitable for preparing overbasedmaterials which can be converted to disperse systems for use in thecompositions of the invention. Similarly, U.S. Pat. Nos. 2,616,904;2,695,910; 2,767,164; 2,767,209; 3,147,232; and 3,274,135 disclose avariety of organic acids suitable for preparing overbased materials aswell as representative examples of overbased products prepared from suchacids. Overbased acids wherein the acid is a phosphorus acid, athiophosphorus acid, phosphorus acid-sulfur acid combination, and sulfuracid prepared from polyolefins are disclosed in U.S. Pat. Nos.2,883,340; 2,915,517; 3,001,981; 3,108,960; and 3,232,883. Overbasedphenates are disclosed in U.S. Pat. Nos. 2,959,551 while overbasedketones are found in U.S. Pat. No. 2,798,852. A variety of overbasedmaterials derived from oil-soluble metal-free, non-tautomeric neutraland basic organic polar compounds such as esters, amines, amides,alcohols, ethers, sulfides, sulfoxides, and the like are disclosed inU.S. Pat. Nos. 2,968,642; 2,971,014; and 2,989,463. Another class ofmaterials which can be overbased are the oil-soluble, nitro-substitutedaliphatic hydrocarbons, particularly nitro-substituted polyolefins suchas polyethylene, polypropylene, polyisobutylene, etc. Materials of thistype are illustrated in U.S. Pat. No. 2,959,551. Likewise, theoil-soluble reaction product of alkylene polyamines such as propylenediamine or N-alkylated propylene diamine with formaldehyde orformaldehyde producing compound (e.g., paraformaldehyde) can beoverbased. Other compounds suitable for overbasing are disclosed in theabove-cited patents or are otherwise well known in the art.

The organic liquids used as the disperse medium in the colloidaldisperse system can be used as solvents for the overbasing process.

The metal compounds used in preparing the overbased materials arenormally the basic salts of metals in Group I-A and Group II-A of thePeriodic Table although other metals such as lead, zinc, manganese,etc., can be used in the preparation of overbased materials. The anionicportion of the salt can be hydroxyl, oxide, carbonate, hydrogencarbonate, nitrate, sulfite, hydrogen sulfite, halide, amide, sulfateetc., as disclosed in the above-cited patents. Preferred overbasedmaterials are prepared from the alkaline earth metal oxides, hydroxides,and alcoholates such as the alkaline earth metal lower alkoxides.

The promoters, that is, the materials which permit the incorporation ofthe excess metal into the overbased material, are also quite diverse andwell known in the art as evidenced by the above-cited patents. Aparticularly comprehensive discussion of suitable promoters is found inU.S. Pat. No. 2,777,874; 2,695,910; and 2,616,904. These include thealcoholic and phenolic promoters which are preferred. The alcoholicpromoters include the alkanols of 1 to about 12 carbon atoms such asmethanol, ethanol, amyl alcohol, octanol, isopropanol, and mixtures ofthese and the like. Phenolic promoters include a variety ofhydroxy-substituted benzenes and naphthalenes. A particularly usefulclass of phenols are the alkylated phenols of the type listed in U.S.Pat. No. 2,777,874, e.g., heptylphenols, octylphenols, and nonylphenols.Mixtures of various promoters are sometimes used.

Suitable acidic materials are also disclosed in the above-cited patents,for example, U.S. Pat. No. 2,616,904. Included within the known group ofuseful acidic materials are liquid acids such as formic acid, aceticacid, nitric acid, sulfuric acid, hydrochloric acid, hydrobromic acid,carbamic acid, substituted carbamic acids, etc. Acetic acid is a veryuseful acidic material although inorganic acidic materials such as HCl,SO₂, SO₃, CO₂, H₂ S, N₂ O₃, etc., are ordinarily employed as the acidicmaterials. Preferred acidic materials are carbon dioxide and aceticacid.

In preparing overbased materials, the material to be overbased, an inertnon-polar organic solvent therefor, the metal base, the promoter and theacidic material are brought together and a chemical reaction ensues. Theexact nature of the resulting overbased product is not known. However,it can be adequately described for purposes of the present specificationas a single phase homogeneous mixture of the solvent and (1) either ametal complex formed from the metal base, the acidic material, and thematerial being overbased and/or (2) an amorphous metal salt formed fromthe reaction of the acidic material with the metal base and the materialwhich is said to be overbased. Thus, if mineral oil is used as thereaction medium, petrosulfonic acid as the material which is overbased,Ca(OH)₂ as the metal base, and carbon dioxide as the acidic material,the resulting overbased material can be described for purposes of thisinvention as an oil solution of either a metal containing complex of theacidic material, the metal base, and the petrosulfonic acid or as an oilsolution of amorphous calcium carbonate and calcium petrolsulfonate.

The temperature at which the acidic material is contacted with theremainder of the reaction mass depends to a large measure upon thepromoting agent used. With a phenolic promoter, the temperature usuallyranges from about 80° C. to 300° C., and preferably from about 100° C.to about 200° C. When an alcohol or mercaptan is used as the promotingagent, the temperature usually will not exceed the reflux temperature ofthe reaction mixture and preferably will not exceed about 100° C.

In view of the foregoing, it should be apparent that the overbasedmaterials may retain all or a portion of the promoter. That is, if thepromoter is not volatile (e.g., an alkyl phenol) or otherwise readilyremovable from the overbased material, at least some promoter remains inthe overbased product. Accordingly, the disperse systems made from suchproducts may also contain the promoter. The presence or absence of thepromoter in the overbased material used to prepare the disperse systemand likewise, the presence or absence of the promoter in the colloidaldisperse systems themselves does not represent a critical aspect of theinvention. Obviously, it is within the skill of the art to select avolatile promoter such as a lower alkanol, e.g., methanol, ethanol,etc., so that the promoter can be readily removed prior to incorporationwith the compositions or drilling fluids of the present invention.

A preferred class of overbased materials used as starting materials inthe preparation of the disperse systems of the present invention are thealkaline earth metal-overbased oil-soluble organic acids, preferablythose containing at least 12 aliphatic carbons although the acids maycontain as few as 8 aliphatic carbons if the acid molecule includes anaromatic ring such as phenol, naphthyl, etc. Representative organicacids suitable for preparing these overbased materials are discussed andidentified in detail in the above-cited patents. Particularly U.S. Pat.Nos. 2,616,904 and 2,777,874 disclose a variety of suitable organicacids. Overbased oil-soluble carboxylic and sulfonic acids areparticularly suitable. Illustrative of the carboxylic acids are palmiticacid, stearic acid, myristic acid, oleic acid, linoleic acid, behenicacid, hexatriacontanoic acid, tetrapropylene-substituted glutaric acid,polyisobutene (M.W.-5000)-substituted succinic acid, polypropylene,(M.W.-10,000)-substituted succinic acid, octadecyl-substituted adipicacid, chlorostearic acid, 9-methylstearic acid, dichlorostearic acid,stearylbenzoic acid, eicosane-substituted naphthoic acid,dilauryldecahydronaphthalene carboxylic acid, didodecyltetralinecarboxylic acid, dioctylcyclohexane carboxylic acid, mixtures of theseacids, their alkali and alkaline earth metal salts, and/or theiranhydrides. Of the oil-soluble sulfonic acids, the mono-, di-, andtri-aliphatic hydrocarbon substituted aryl sulfonic acids and thepetroleum sulfonic acids (petrolsulfonic acids) are particularlypreferred. Illustrative examples of suitable sulfonic acids includemahogany sulfonic acids, petrolatum sulfonic acids,monoeicosane-substituted naphthalene sulfonic acids dodecylbenzenesulfonic acids, didodecylbenzene sulfonic acids, dinonylbenzene sulfonicacids, cetylchlorobenzene sulfonic acids, dilauryl beta-naphthalenesulfonic acids, the sulfonic acid derived by the treatment ofpolyisobutene having a molecular weight of 1500 with chlorosulfonicacid, nitronaphthalene sulfonic acid, paraffin wax sulfonic acid,cetylcyclopentane sulfonic acid, lauryl-cyclohexanesulfonic acids,polyethylene (M.W.-750) sulfonic acids, etc. Obviously, it is necessarythat the size the number of aliphatic groups on the aryl sulfonic acidsbe sufficient to render the acids soluble. Normally the aliphatic groupswill be alkyl and/or alkenyl groups such that the total number ofaliphatic carbons is at least 12.

Within this preferred group of overbased carboxylic and sulfonic acids,the barium, and calcium overbased mono-, di-, and tri-alkylated benzeneand naphthalene (including hydrogenated forms thereof), petrosulfonicacids, and higher fatty acids are especially preferred. Illustrative ofthe synthetically produced alkylated benzene and naphthalene sulfonicacids are those containing alkyl substituents having from 8 to about 30carbon atoms therein. Such acids include di-isododecyl-benzene sulfonicacid, wax-substituted phenol sulfonic acid, wax-substituted benzenesulfonic acids, polybutene-substituted sulfonic acid,cetyl-chlorobenzene sulfonic acid, di-cetylnaphthalene sulfonic acid,di-lauryldiphenylether sulfonic acid, di-isononylbenzene sulfonic acid,di-isooctadecylbenzene sulfonic acid, stearylnaphthalene sulfonic acid,and the like. The petroleum sulfonic acids are a well known artrecognized class of materials which have been used as starting materialsin preparing overbased products since the inception of overbasingtechniques as illustrated by the above patents. Petroleum sulfonic acidsare obtained by treating refined or semi-refined petroleum oils withconcentrated or fuming sulfuric acid. These acids remain in the oilafter the settling out of sludges. These petroleum sulfonic acids,depending on the nature of the petroleum oils from which they areprepared, are oil-soluble alkane sulfonic acids, alkyl-substitutedcycloaliphatic sulfonic acids including cycloalkyl sulfonic acids andcycloalkene sulfonic acids, and alkyl, alkaryl, or aralkyl substitutedhydrocarbon aromatic sulfonic acids including single and condensedaromatic nuclei as well as partially hydrogenated forms thereof.Examples of such petrosulfonic acids include mahogany sulfonic acid,white oil sulfonic acid, petrolatum sulfonic acid, petroleum naphthenesulfonic acid, etc. This preferred group of aliphatic fatty acidsincludes the saturated and unsaturated higher fatty acids containingfrom about 12 to about 30 carbon atoms. Illustrative of these acids arelauric acid, palmitic acid, oleic acid, linoleic acid, linoleic acid,oleostearic acid, stearic acid, myristic acid, and undecalinic acid,alphachlorostearic acid, and alpha-nitrolauric acid.

As shown by the representative examples of the preferred classes ofsulfonic and carboxylic acids, the acids may contain non-hydrocarbonsubstituents such as halo, nitro, alkoxy, hydroxyl, and the like.

It is desirable that the overbased materials used to prepare thedisperse system have a metal ratio of at least about 3.5 and preferablyat least about 4.5. An especially suitable group of the preferredsulfonic acid overbased materials has a metal ratio of at least about 7.While overbased materials having metal ratios as high as 75 have beenprepared and can be used, normally the maximum metal ratio will notexceed about 30 and, in most cases, not more than about 20.

The overbased materials used in preparing the disperse systems utilizedin the compositions and drilling fluids of the present invention usuallycontain from about 10% to about 70% by weight of metal-containingcomponents. As explained hereafter, the exact nature of thesemetal-containing components is not known. While not wishing to be boundby theory, it is believed that the metal base, the acidic material, andthe organic material being overbased form a metal complex, this complexbeing the metal-containing component of the overbased material. On theother hand, it has also been postulated that the metal base and theacidic material form amorphous metal compounds which are dissolved inthe inert organic reaction medium and the material which is said to beoverbased. The material which is overbased may itself be ametal-containing compound, e.g., a carboxylic or sulfonic acid metalsalt. In such a case, the metal containing components of the overbasedmaterial would be both the amorphous compounds and the acid salt. Theremainder of the overbased materials consist essentially of the inertorganic reaction medium and any promoter which is not removed from theoverbased product. For purposes of this patent application, the organicmaterial which is subjected to overbasing is considered a part of themetal-containing components. Normally, the liquid reaction mediumconstitutes at least about 30% by weight of the reaction mixtureutilized to prepare the overbased materials.

As mentioned above, the colloidal disperse systems used in thecomposition of the present invention are prepared by homogenizing a"conversion agent" and the overbased starting material. Homogenizationis achieved by vigorous agitation of the two components, preferably atthe reflux temperature or a temperature slightly below the refluxtemperature. The relfux temperature normally will depend upon theboiling point of the conversion agent. However, homogenization may beachieved within the range of about 25° C. to about 200° C. or slightlyhigher. Usually, there is no real advantage in exceeding about 150° C.

The concentration of the conversion agent necessary to achieveconversion of the overbased material is usually within the range of fromabout 1% to about 80% based upon the weight of the overbased materialexcluding the weight of the inert organic solvent and any promoterpresent therein. Preferably at least about 10% and usually less thanabout 60% by weight of the conversion agent is employed. Concentrationsbeyond 60% appear to afford no additional advantages.

The terminology "conversion agent" as used herein is intended todescribe a class of very diverse materials which possess the property ofbeing able to convert the Newtonian homogeneous, single-phase, overbasedmaterials into non-Newtonian colloidal disperse systems. The mechanismby which conversion is accomplished is not completely understood.However, with the exception of carbon dioxide, these conversion agentsall possess active hydrogens. The conversion agents include loweraliphatic carboxylic acids, water, aliphatic alcohols, cycloaliphaticalcohols, arylaliphatic alcohols, phenols, ketones, aldehydes, amines,boron acids, phosphorus acids, and carbon dioxide. Mixtures of two ormore of these conversion agents are also useful. Particularly usefulconversion agents are discussed below.

The lower aliphatic carboxylic acids are those containing less thanabout 8 carbon atoms in the molecule. Examples of this class of acidsare formic acid, acetic acid, propionic acid, butyric acid, valericacid, isovaleric acid, isobutyric acid, caprylic acid, heptanoic acid,chloroacetic acid, dichloroacetic acid, trichloroacetic acid, etc.Formic acid, acetic acid, and propionic acid, are preferred with aceticacid being especially suitable. It is to be understood that theanhydrides of these acids are also useful and, for the purposes of thespecification and claims of this invention, the term acid is intended toinclude both the acid per se and the anhydride of the acid.

Useful alcohols include aliphatic, cycloaliphatic, and arylaliphaticmono- and polyhydroxy alcohols. Alcohols having less than about 12carbons are especially useful while the lower alkanols, i.e., alkanolshaving less than about 8 carbon atoms are preferred for reasons ofeconomy and effectiveness in the process. Illustrative are the alkanolssuch as methanol, ethanol, isopropanol, n-propanol, isobutanol, tertiarybutanol, isooctanol, dodecanol, n-pentanol, etc.; cycloalkyl alcoholsexemplified by cyclopentathol, cyclohexanol, 4-methylcyclohexanol,2-cyclohexylethanol, cyclopentylmethanol, etc.; phenyl aliphaticalkanols such as benzyl alcohol, 2-phenylethanol, and cinnamyl alcohol;alkylene glycols of up to about 6 carbon atoms and mono-lower alkylethers thereof such as monomethylether of ethylene glycol, diethyleneglycol, ethylene glycol, trimethylene glycol, hexamethylene glycol,triethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, glycerol, andpentaerythritol.

The use of a mixture of water and one or more of the alcohols isespecially effective for converting the overbased material to colloidaldisperse systems. Such combinations often reduce the length of timerequired for the process. Any water-alcohol combination is effective buta very effective combination is a mixture of one or more alcohols andwater in a weight ratio of alcohol to water of from about 0.05:1 toabout 24:1. Preferably, at least one lower alkanol is present in thealcohol component of these water-alkanol mixtures. Water-alkanolmixtures wherein the alcoholic portion is one or more lower alkanols areespecially suitable.

Phenols suitable for use as conversion agents include phenol, naphthol,ortho-cresol, para-cresol, catechol, mixtures of cresol,para-tert-butylphenol, and other lower alkyl substituted phenols,meta-polyisobutene (M.W.-350)-substituted phenol, and the like.

Other useful conversion agents include lower aliphatic aldehydes andketones, particularly lower alkyl aldehydes and lower alkyl ketones suchas acetaldehydes, propionaldehydes, butyraldehydes, acetone, methylethylketone, diethyl ketone. Various aliphatic, cycloaliphatic, aromatic, andheterocyclic amines are also useful providing they contain at least oneamino group having at least one active hydrogen attached thereto.Illustrative of these amines are the mono- and di-alkylamines,particularly mono- and di-lower alkylamines, such as methylamine,ethylamine, propylamine, dodecylamine, methyl ethylamine, diethylamine;the cycloalkylamines such as cyclohexylamine, cyclopentylamine, and thelower alkyl substituted cycloalkylamines such as3-methylcyclohexylamine; 1,4-cyclohexylenediamine; arylamines such asaniline, mono-, di-, and tri-, lower alkyl-substituted phenyl amines,naphthylamines, 1,4-phenylene diamines; lower alkanol amines such asethanolamine and diethanolamine; alkylenediamines such as ethylenediamine, triethylene tetramine, propylene diamines, octamethylenediamines; and heterocyclic amines such as piperazine,4-aminoethylpiperazine, 2-octadecyl-imidazoline, and oxazolidine. Boronacids are also useful conversion agents and include boronic acids (e.g.,alkyl-B(OH)₂ or aryl-B(OH₂)), boric acid (i.e., H₃ BO₃), tetraboricacid, metaboric acid, and esters of such boron acids.

The phosphorus acids are useful conversion agents and include thevarious alkyl and aryl phosphinic acids, phosphinus acids, phosphonicacids, and phosphonous acids. Phosphorus acids obtained by the reactionof lower alkanols or unsaturated hydrocarbons such as polyisobuteneswith phosphorus oxides and phosphorus sulfides are particularly useful,e.g., P₃ O₅ and P₂ S₅.

Carbon dioxide can be used as the conversion agent. However, it ispreferable to use this conversion agent in combination with one or moreof the foregoing conversion agents. For example, the combination ofwater and carbon dioxide is particularly effective as a conversion agentfor transforming the overbased materials into a colloidal dispersesystem.

As previously mentioned, the overbased materials are single phasehomogeneous systems. However, depending on the reaction conditions andthe choice of reactants in preparing the overbased materials, theresometimes are present in the product insoluble contaminants. Thesecontaminants are normally unreacted basic materials such as calciumoxide, barium oxide, calcium hydroxide, barium hydroxide, or other metalbase materials used as a reactant in preparing the overbased material.It has been found that a more uniform colloidal disperse system resultsif such contaminants are removed prior to homogenizing the overbasedmaterial with the conversion agents. Accordingly, it is preferred thatany insoluble contaminants in the overbased materials be removed priorto converting the material in the colloidal disperse system. The removalof such contaminants is easily accomplished by conventional techniquessuch as filtration or centrifugation. It should be understood, however,that the removal of these contaminants, while desirable for reasons justmentioned, is not an absolute essential aspect of the invention anduseful products can be obtained when overbased materials containinginsoluble contaminants are converted to the colloidal disperse systems.

The conversion agents or a proportion thereof may be retained in thecolloidal disperse system. The conversion agents are, however, notessential components of these disperse systems and it is usuallydesirable that as little of the conversion agents as possible beretained in the disperse systems. Since these conversion agents do notreact with the overbased material in such a manner as to be permanentlybound thereto through some type of chemical bonding, it is normally asimple matter to remove a major proportion of the conversion agents and,generally, substantially all of the conversion agents. Some of theconversion agents have physical properties which make them readilyremovable from the disperse systems. Thus, most of the free carbondioxide gradually escapes from the disperse system during thehomogenization process or upon standing thereafter. Since the liquidconversion agents are generally more volatile than the remainingcomponents of the disperse system, they are readily removable byconventional devolatilization techniques, e.g., heating, heating atreduced pressures, and the like. For this reason, it may be desirable toselect conversion agents which will have boiling points which are lowerthan the remaining components of the disperse system. This is anotherreason why the lower alkanols, mixtures thereof, and lower alkanol-watermixtures are preferred conversion agents.

Again, it is not essential that all of the conversion agent be removedfrom the disperse systems. However, from the standpoint of achievinguniform results, it is generally desirable to remove the conversionagents, particularly where they are volatile. In some cases, the liquidconversion agents may facilitate the mixing of the colloidal dispersesystem with the aqueous compositions of the invention. In such cases, itis advantageous to permit the conversion agents to remain in thedisperse system until it is mixed with such aqueous compositions.Thereafter, the conversion agents can be removed from such compositionsby conventional devolatilization techniques if desired.

To better illustrate the colloidal disperse systems utilized in theinvention, the procedure for preparing a preferred system is describedbelow:

As stated above, the essential materials for preparing an overbasedproduct are (1) the organic material to be overbased, (2) an inert,non-polar organic solvent for the organic material, (3) a metal base,(4) a promoter, and (5) an acidic material. In this example, thesematerials are (1) calcium petrosulfonate, (2) mineral oil, (3) calciumhydroxide, (4) a mixture of methanol, isobutanol, and n-pentanol, and(5) carbon dioxide.

A reaction mixture of 1305 grams of calcium sulfonate having a metalratio of 2.5 dissolved in mineral oil, 220 grams of methyl alcohol, 72grams of isobutanol, and 38 grams of n-phenatanol is heated to 35° C.and subjected to the following operating cycle four times: mixing with143 grams of 90% calcium hydroxide and treating the mixture with carbondioxide until it has a base number of 32-39. The resulting product isthen heated to 155° C. during a period of nine hours to remove thealcohols and then filtered at this temperature. The filtrate is acalcium overbased petrosulfonate having a metal ratio of 12.2.

A mixture of 150 parts of the foregoing overbased material, 15 parts ofmethyl alcohol, 10.5 parts of n-pentanol and 45 parts of water is heatedunder reflux conditions at 71°-74° C. for 13 hours. The mixture becomesa gel. It is then heated to 144° C. cover a period of six hours anddiluted with 126 parts of mineral oil having a viscosity of 2000 SUS at100° F. and the resulting mixture heated at 144° C. for an additional4.5 hours with stirring. This thickened product is a colloidal dispersesystem of the type contemplated by the present invention.

The disperse systems are characterized by three essential components:(1) solid, metal-containing particles, (2) an inert, non-polar, organicliquid which functions as the disperse medium, and (3) an organiccompound which is soluble in the disperse medium and the molecules ofwhich are characterized by a hydrophobic portion and at least one polarsubstituent. In the colloidal disperse system described immediatelyabove, these components are as follows: (1) calcium carbonate in theform of solid particles, (2) mineral oil, and (3) calciumpetrosulfonate.

From the foregoing example, it is apparent that the solvent for thematerial which is overbased becomes the colloidal disperse medium or acomponent thereof. Of course, mixtures of other inert liquids can besubstituted for the mineral oil or used in conjunction with the mineraloil prior to forming the overbased material.

It is also readily seen that the solid, metal-containing particlespossess the same chemical composition as would the reaction products ofthe metal base and the acidic material used in preparing the overbasedmaterials. Thus, the actual chemical identity of the metal-containingparticles depends upon both the particular metal base or bases employedand the particular acidic material or materials reacted therewith. Forexample, if the metal base used in preparing the overbased material werebarium oxide and if the acidic material was a mixture of formic andacetic acids, the metal-containing particles would be barium formatesand barium acetates.

However, the physical characteristics of the metal-containing particlesformed in the conversion step are quite different from the physicalcharacteristics of any particles present in the homogeneous,single-phase overbased material which is subjected to the conversion.Particularly, such physical characteristics as particle size andstructure are quite different. The solid, metal-containing particles ofthe colloidal disperse systems are of a size sufficient for detection byX-ray diffraction. The overbased material prior to conversion are notcharacterized by the presence of these detectable particles.

X-ray diffraction and electron microscope studies have been made of bothoverbased organic materials and colloidal disperse systems preparedtherefrom. These studies establish the presence in the disperse systemsof the solid metal-containing salts. For example, in the disperse systemprepared herein above, the calcium carbonate is present as solid calciumcarbonate having a particle size of about 40 to 50 A. (unit particlesize) and interplanar spacing (dA.) of 3.035. But X-ray diffractionstudies of the overbased material from which it was prepared indicatethe absence of calcium carbonate of this type. In fact, calciumcarbonate present as such, if any, appears to be amorphous and insolution. While not wishing to be bound by theory, it appears thatconversion permits particle formation and growth. That is, theamorphous, metal-containing apparently dissolved salts or complexespresent in the overbased material form solid, metal-containing particleswhich by a process of particle growth become colloidal particles. Thus,in the above example, the dissolved amorphous calcium carbonate salt orcomplex is transformed into solid particles which then "grow". In thisexample, they grow to a size of 40 to 50 A. In many cases, theseparticles apparently are crystallites. Regardless of the correctness ofthe postulated mechanism for particle formation the fact remains that noparticles of the type predominant in the disperse systems are found inthe overbased materials from which they are prepared. Accordingly, theyare unquestionably formed during conversion.

As these solid metal-containing particles formed come into existence,they do so as pre-wet, pre-dispersed solid particles which areinherently uniformly distributed throughout the other components of thedisperse system. The liquid disperse medium containing these pre-wetdispersed particles is readily incorporated into the compositions anddrilling fluids of the invention thus facilitating the uniformdistribution of the particles throughout such compositions and drillingfluids. This pre-wet, pre-dispersed character of the solidmetal-containing particles resulting from their formation is, thus, animportant feature of the disperse systems.

In the foregoing example, the third component of the disperse system(i.e., the organic compound which is soluble in the disperse medium andwhich is characterized by molecules having a hydrophobic portion and apolar substituent) is calcium petrosulfonate, ##STR4## wherein R₁ is theresidue of the petrosulfonic acid. In this case, the hydrophobic portionof the molecule is the hydrocarbon moiety of petrosulfonic, i.e., -R₁.The polar substituent is the metal salt moiety, ##STR5##

The hydrophobic portion of the organic compound is a hydrocarbon radicalor a substantially hydrocarbon radical containing at least about 12aliphatic carbon atoms. Usually the hydrocarbon portion is an aliphaticor cycloaliphatic hydrocarbon radical although aliphatic orcycloaliphatic substituted aromatic hydrocarbon radicals are alsosuitable. In other words, the hydrophobic portion of the organiccompound is the residue of the organic material which is overbased minusits polar substituents. For example, if the material to be overbased isa carboxylic acid, sulfonic acid, or phosphorus acid, the hydrophobicportion is the residue of these acids which would result from theremoval of the acid functions. Similarly, if the material to beoverbased is a phenol, a nitro-substituted polyolefin, or an amine, thehydrophobic portion of the organic compound is the radical resultingfrom the removal of the hydroxyl, nitro, or amino group respectively. Itis the hydrophobic portion of the molecule which renders the organiccompound soluble in the solvent used in the overbasing process and laterin the disperse medium.

Obviously, the polar portion of these organic compounds are the polarsubstituents such as the acid salt moiety discussed above. When thematerial to be overbased contains polar substituents which will reactwith the basic metal compound used in overbasing, for example, acidgroups such as carboxy, sulfino, hydroxysulfonyl, and phosphorus acidgroups or hydroxyl groups, the polar substituent of the third componentis the polar group formed from the reaction. Thus, the polar substituentis the corresponding acid metal salt group or hydroxyl group metalderivative, e.g., an alkali or alkaline earth metal sulfonate,carboxylate, sulfinate, alcoholate, or phenate.

On the other hand, some of the materials to be overbased contain polarsubstituents which ordinarily do not react with metal bases. Thesesubstituents include nitro, amino, ketocarboxyl, carboalkoxy, etc. Inthe disperse systems derived from overbased materials of this type thepolar substituents in the third component are unchanged from theiridentity in the material which was originally overbased.

The identity of the third essential component of the disperse systemdepends upon the identity of the starting materials (i.e., the materialto be overbased and the metal base compound) used in preparing theoverbased material. Once the identity of these starting materials isknown, the identity of the third component in the colloidal dispersesystem is automatically established. Thus, from the identity of theoriginal material, the identity of the hydrophobic portion of the thirdcomponent in the disperse system is readily established as being theresidue of that material minus the polar substituents attached thereto.The identity of the polar substituents on the third component isestablished as a matter of chemistry. If the polar groups on thematerial to be overbased undergo reaction with the metal base, forexample, if they are acid functions, hydroxy groups, etc., the polarsubstituent in the final product will correspond to the reaction productof the original substituent and the metal base. On the other hand, ifthe polar substituent in the material to be overbased is one which doesnot react with metal bases, then the polar substituent of the thirdcomponent is the same as the original substituent.

As previously mentioned, this third component can orient itself aroundthe metal-containing particles to form micellar colloidal particles.Accordingly, it can exist in the disperse system as an individual liquidcomponent dissolved in the disperse medium or it can be associated withthe metal-containing particles as a component of micellar colloidalparticles.

Examples 1-66 illustrate various overbased materials and colloidaldisperse systems prepared from these overbased materials. Unlessotherwise indicated, "percentages" and "parts" refer to percent byweight and parts by weight. Where temperatures exceed the boiling pointsof the components of the reaction mixture, obviously reflux conditionsare employed unless the reaction products are being heated to removevolatile components.

Examples 1 through 23 are directed to the preparation of Newtonianoverbased materials illustrative of the types which can be used toprepare non-Newtonian colloidal disperse systems. The term "naphtha" asused in the following examples refers to petroleum distillates boilingin the range of about 90° C. to about 150° C. and usually designatedVarnish Maker's and Painter's Naphtha.

EXAMPLE 1

To a mixture of 3.245 parts (12.5 equivalents) of a mineral oil solutionof barium petroleum sulfonate (sulfate ash of 7.6%), 32.5 parts ofoctylphenol, 197 parts of water, there is added 73 parts of barium oxidewithin a period of 30 minutes at 57°-84° C. The mixture is heated at100° C. for one hour to remove substantially all water and blown with 75parts of carbon dioxide at 133° to 170° C. within a period of threehours. A mixture of 1,000 parts of the above carbonated intermediateproduct, 121.8 parts of octylphenol, and 234 parts of barium hydroxideis heated at 100° C. and then at 150° C. for one hour. The mixture isthen blown with carbon dioxide at 150° C. for one hour at a rate of 3cubic feet per hour. The carbonated product is filtered and the filtratehas a sulfate ash content of 39.8% and a metal ratio of 9.3

EXAMPLE 2

To a mixture of 3,245 parts (12.5 equivalents) of barium petroleumsulfonate, 1,460 parts (7.5 equivalents) of heptylphenol, and 2,100parts of water in 8,045 parts of mineral oil there is added at 180° C.7,400 parts (96.5 equivalents) of barium oxide. The addition of bariumoxide causes the temperature to rise to 143° C. which temperature ismaintained until all the water has been distilled. The mixture is thenblown with carbon dioxide until it is substantially neutral. The productis diluted with 5,695 parts of mineral oil and filtered. The filtratehas a barium sulfate ash content of 30.5% and a metal ratio of 8.1.

EXAMPLE 3

A mixture of 1,285 parts (1.0 equivalent) of 40% barium petroleumsulfonate and 500 milliliters (12.5 equivalents) of methanol is stirredat 55°-60° C. while 301 parts (3.9 equivalents) of barium oxide is addedportion-wise over a period of one hour. The mixture is stirred anadditional two hours at 45°-55° C. then treated with carbon dioxide at55°-65° C. for two hours. The resulting mixture is freed of methanol byheating to 150° C. The residue is filtered through a siliceous filteraid, the clear, brown filtrate analyzing as: sulfate ash, 33.2%;slightly acid; metal ratio, 4.7.

EXAMPLE 4

(a) To a mixture of 1,145 parts of a mineral oil solution of a 40%solution of barium mahogany sulfonates (1.0 equivalent) and 100 parts ofmethyl alcohol at 55° C., there is added 220 parts of barium oxide whilethe mixture is being blown with carbon dioxide at a rate of 2 to 3 cubicfeet per hour. To this mixture there is added an additional 78 parts ofmethyl alcohol and then 460 parts of barium oxide while the mixture isblown with carbon dioxide. The carbonated product is heated to 150°C.for one hour and filtered. The filtrate has a barium sulfate ash contentof 53.8% and a metal ratio of 8.9.

(b) A carbonated basic metal salt is prepared in accordance with theprocedure of (a) except that a total of 16 equivalents of barium oxideis used per equivalent of the barium mahogany sulfonate. The product hasa metal ratio of 13.4.

EXAMPLE 5

A mixture of 520 parts of a mineral oil, 480 parts of a sodium petroleumsulfonate (molecular weight of 480), and 84 parts of water is heated at100° C. for four hours. The mixture is then heated with 86 parts of a76% aqueous solution of calcium chloride and 72 parts of lime (90%purity) at 100° C. for two hours, dehydrated by heating to a watercontent of less than 0.5%, cooled to 50° C., mixed with 130 parts ofmethyl alcohol, and then blown with carbon dioxide at 50° C. untilsubstantially neutral. The mixture is then heated to 150° C. to removethe methyl alcohol and water and the resulting oil solution of the basiccalcium sulfonate filtered. The filtrate is found to have a calciumsulfate ash content of 16% and a metal ratio of 2.5.

A mixture of 1,305 parts of the above carbonated calcium sulfonate, 930parts of mineral oil, 220 parts of methyl alcohol, 72 parts of isobutylalcohol, and 38 parts of primary amyl alcohol is prepared, heated to 35°C., and subjected to the following operating cycle four times: mixingwith 143 parts of 90% calcium hydroxide and treating the mixture withcarbon dioxide until it has a base number of 32-39. The resultingproduct is then heated to 155° C. during a period of nine hours toremove the alcohols and filtered through a siliceous filter aid at thistemperature. The filtrate has a calcium sulfate ash content of 39.5% anda metal ratio of 12.2.

EXAMPLE 6

A basic metal salt is prepared by the procedure described in Example 5except that the slightly basic calcium sulfonate having a metal ratio of2.5 is replaced with a mixture of that calcium sulfonate (280 parts) andtall oil acid (970 parts having an equivalent weight of 340) and thatthe total amount of calcium hydroxide used is 930 parts. The resultinghighly basic metal salt of the process has a calcium sulfate ash contentof 48%, a metal ratio of 7.7, and an oil content of 31%.

EXAMPLE 7

A highly basic metal salt is prepared by the procedure of Example 5except that the slightly basic calcium sulfonate starting materialhaving a metal ratio of 2.5 is replaced with tall oil acids (1,250 partshaving an equivalent weight of 340) and the total amount of calciumhydroxide used is 772 parts. The resulting highly basic metal salt has ametal ratio of 5.2, a calcium sulfate ash content of 41%, and an oilcontent of 33%.

EXAMPLE 8

A normal calcium mahogany sulfonate is prepared by metathesis of a 60%oil solution of sodium mahogany sulfonate (750 parts) with a solution of67 parts of calcium chloride and 63 parts of water. The reaction mass isheated for four hours at 90° to 100° C. to effect the conversion of thesodium mahogany sulfonate to calcium mahogany sulfonate. Then 54 partsof lime is added and the whole is heated to 150° C. over a period offive hours. When the whole has cooled to 40° C., 98 parts of methanol isadded and 152 parts of carbon dioxide is introduced over a period of 20hours at 42°-43° C. Water and alcohol are then removed by heating themass of 150° C. The residue in the reaction vessel is diluted with 100parts of low viscosity mineral oil. The filtered oil solution of thedesired carbonated calcium sulfonate overbased material has thefollowing analysis: sulfate ash content, 16.4%; neutralization number,0.6 (acidic); and a metal ratio of 2.50. By adding barium or calciumoxide or hydroxide to this product with subsequent carbonation, themetal ratio can be increased to a ratio of 3.5 or greater as desired.

EXAMPLE 9

A mixture comprising 1,595 parts of the overbased material of Example 7(1.54 equivalents based on sulfonic acid anion), 167 parts of thecalcium phenate prepared as indicated below (0.19 equivalent), 616 partsof mineral oil, 157 parts of 91% calcium hydroxide (3.86 equivalents),288 parts of methanol, 88 parts of isobutanol, and 56 parts of mixedisomeric primary amyl alcohols (containing about 65% normal amyl, 3%isoamyl and 32% of 2-methyl-1-butyl alcohols) is stirred vigorously at40° C. and 25 parts of carbon dioxide is introduced over a period of twohours at 40°-50° C. Thereafter, three additional portions of calciumhydroxide, each amounting to 157 parts, are added and each such additionis followed by the introduction of carbon dioxide as previouslyillustrated. After the fourth calcium hydroxide addition and thecarbonation step is completed, the reaction mass is carbonated for anadditional hour at 43°-47° C. to reduce neutralization number of themass to 4.0 (basic). The substantially neutral, carbonated reactionmixture is freed from alcohol and any water reaction by heating to 150°C. and simultaneously blowing it with nitrogen. The residue in thereaction vessel is filtered. The filtrate, an oil solution of thedesired substantially neutral, carbonated calcium sulfonate overbasedmaterial of high metal ratio, shows the following analysis: sulfate ashcontent, 41.11%; neutralization number 0.9 (basic); and a metal ratio of12.55.

The calcium phenate used above is prepared by adding 2,250 parts ofmineral oil, 960 parts (5 moles) of heptylphenol, and 50 parts of waterinto a reaction vessel and stirring at 25° C. The mixture is heated to40° C. and 7 parts of calcium hydroxide and 231 parts (7 moles) of 91%commercial paraformaldehyde is added over a period of one hour. Thewhole is heated to 80° C. and 200 additional parts of calcium hydroxide(making a total of 207 parts or 5 moles) is added over a period of onehour at 80°-90° C. The whole is heated to 150° C. and maintained at thattemperature for 12 hours while nitrogen is blown through the mixture toassist in the removal of water. If foaming is encountered, a few dropsof polymerized dimethyl silicone foam inhibitor may be added to controlthe foaming. The reaction mass is then filtered. The filtrate, a 33.6%oil solution of the desired calcium phenate of heptylphenol-formaldehydecondensation product is found to contain 7.56% sulfate ash.

EXAMPLE 10

A mixture of 574 parts (0.5 equivalents) of 40% barium petroleumsulfonate, 98 parts (1.0 equivalent) of furfuryl alcohol, and 762 partsof mineral oil is heated with stirring at 100° C. for an hour, thentreated portionwise over a 15-minute period with 230 parts (3.0equivalents) of barium oxide. During this latter period, the temperaturerises to 120° C. (because of the exothermic nature of the reaction ofbarium oxide and the alcohol). The mixture then is heated to 150°-160°C. for an hour, and treated subsequently at this temperature for 1.5hours with carbon dioxide. The materials concentrated by heating to atemperature of 150° C. at a pressure of 10 mm. Hg. and thereafterfiltered to yield a clear, oil-soluble filtrate having the followinganalysis: sulfate ash content, 21.4%; neutralization number, 2.6(basic); and a metal ratio of 6.1.

EXAMPLE 11

To a mixture of 1,614 parts (3 equivalents) of a polyisobutenyl succinicanhydride (prepared by the reaction of a chlorinated polyisobutenehaving an average chlorine content of 4.3% and an average of 67 carbonatoms with maleic anhydride at about 200° C.), 4,313 parts of mineraloil, 345 parts (1.8 equivalents) of heptylphenol, and 200 parts ofwater, at 80° C., there is added 1,038 parts (24.7 equivalents) oflithium hydroxide monohydrate over a period of 0.75 hour while heatingto 105° C. Isooctanol (75 parts) is added while the mixture is heated to150° C. over a 1.5-hour period. The mixture is maintained at 150°-170°C. and blown with carbon dioxide at a rate of four cubic feet per hourfor 3.5 hours. The reaction mixture is filtered through a filter aid andthe filtrate is the desired product having a sulfate ash content of18.9% and a metal ratio of 8.0.

EXAMPLE 12

A mixture of 244 parts (0.87 equivalent) of oleic acid, 180 parts ofprimary isooctanol, and 400 parts of mineral oil is heated to 70° C.whereupon 172.6 parts (2.7 equivalents) of cadmium oxide is added. Themixture is heated for three hours at a temperature of 150° to 160° C.while removing water. Barium hydroxide monohydrate (324 parts, 3.39equivalents) is then added to the mixture over a period of one hourwhile continuing to remove water by means of a side-arm water trap.Carbon dioxide is blown through the mixture at a temperature of from150°-160° C. until the mixture is slightly acidic to phenolphthalein.Upon completion of the carbonation, the mixture is stripped to atemperature of 150° C. at 35 mm. Hg. to remove substantially all theremaining water and alcohol. The residue is the desired overbasedproduct containing both barium and cadmium metal.

EXAMPLE 13

The procedure of Example 10 is repeated except that the barium sulfonateis replaced by an equivalent amount of potassium sulfonate, andpotassium oxide is used in lieu of the barium oxide resulting in thepreparation of the corresponding potassium overbased material.

EXAMPLE 14

To a mixture of 423 parts (1.0 equivalent) of sperm oil, 124 parts (0.6equivalent) of heptylphenol, 500 parts of mineral oil, and 150 parts ofwater there are added 308 parts (4.0 equivalents) of barium oxide. Thetemperature of the mixture is 70° C. during such addition. This mixtureis heated at reflux temperature for one hour, dried by heating at about150° C. and thereafter carbonated by treatment with carbon dioxide atthe same temperature until the reaction mass was slightly acidic.Filtration yields a clear, light brown, non-viscous overbased liquidmaterial having the following analysis: sulfate ash content, 32.0%;neutralization number 0.5 (basic); metal ratio, 6.5.

EXAMPLE 15

A mixture of 6000 parts of a 30% solution of barium petroleum sulfonate(sulfate ash 7.6%), 348 parts of paratertiary butylphenol, and 2,911parts of water are heated to a temperature 60° C. while slowly adding1,100 parts of barium oxide and raising the temperature to 94°-98° C.The temperature is held within this range for about one hour and thenslowly raised over a period of 7.5 hours to 150° C. and held at thislevel for an additional hour assuring substantial removal of all water.The resulting overbased material is a brown liquid having the followinganalysis: sulfate ash content, 26.0%; metal ratio, 4.35.

This product is then treated with SO₂ until 327 parts of the masscombined with the overbased material. The product thus obtained has aneutralization number of zero. The SO₂ -treated material is liquid andbrown in color.

1000 parts of the SO₂ -treated overbased material produced according tothe preceding paragraph is mixed with 286 parts of water and heated to atemperature of about 60° C. Subsequently, 107.5 parts of barium oxideare added slowly and the temperature is maintained at 94°-98° C. for onehour. Then the total reaction mass is heated to 150° C. over a1-1/16-hour period and held there for a period of one hour. Theresulting overbased material is purified by filtration, the filtratebeing a brown, liquid overbased material having the following analysis:sulfate ash content, 33.7%; basic number, 38.6; metal ratio, 6.3.

EXAMPLE 16

(a) A polyisobutylene having a molecular weight of 700-800 is preparedby the aluminum chloride-catalyzed polymerization of isobutylene at0°-30° C., is nitrated with a 10% excess (1.1 moles) of 70% aqueousnitric acid at 70°-75° C. for four hours. The volatile components of theproduct mixture are removed by heating to 75° C. at a pressure of 75 mm.Hg. To a mixture of 151 parts (0.19 equivalent) of this nitratedpolyisobutylene, 113 parts (0.6 equivalent) of heptylphenol, 155 partsof water, and 2,057 parts of mineral oil there is added 612 parts (8equivalents) of barium oxide. The mixture is at 70° C. during suchaddition. This mixture is heated at 150° C. for an hour, then treatedwith carbon dioxide at this same temperature until the mixture isneutral (phenolphthalein indicator; ASTM D-974-53T procedure at 25° C.;a measurement of the degree of conversion of the metal reactant, i.e.,barium oxide, bicarbonation). The product mixture is filtered andfiltrate has the following analysis; sulfate ash content, 27.6%; percentN, 0.06; and metal ratio, 9.

(b) A mixture of 611 parts (0.75 mole) of the nitrated polyisobutyleneof part (a), 96 parts (0.045 mole) of heptylphenol, 2,104 parts ofmineral oil, 188 parts of water and 736 parts (4.8 moles) of bariumoxide is heated at reflux temperature for one hour. The water isvaporized and carbon dioxide passed into the mixture at 150° C. untilthe mixture is no longer basic. This carbonated mixture is filtered andthe clear fluid filtrate has the following analysis; sulfate ashcontent, 26.3%; percent N, 0.15; base number 2.4; metal ratio 6.7.

EXAMPLE 17

A mixture of 630 parts (2 equivalents) of a rosin amine (consistingessentially of dehydroabietyl amine) having a nitrogen content of 44%and 245 parts (1.2 equivalents) of heptylphenol having a hydroxylcontent of 8.3% is heated to 90° C. and thereafter mixed with 230 parts(3 equivalents) of barium oxide at 90°-140° C. The mixture is purgedwith nitrogen at 140° C. A 600-part portion is diluted with 400 parts ofmineral oil and filtered. The filtrate is blown with carbon dioxide,diluted with benzene, heated to remove the benzene, mixed with xylene,and filtered. The filtrate, a 20% xylene solution of the product, has abarium sulfate ash content of 25.1%, a nitrogen content of 2%, and areflux base number of 119.

The term "reflux base number" refers to the basicity of the metalcomposition and is expressed in terms of milligrams of KOH which areequivalent to one gram of the composition.

EXAMPLE 18

To a mixture of 408 parts (2 equivalents) of heptylphenol having ahydroxy content of 8.3% and 264 parts of xylene there is added 383 parts(5 equivalents) of barium oxide in small increments at 85°-110° C.Thereafter, 6 parts of water added and the mixture is carbonated at100°-130° C. and filtered. The filtrate is heated to 100° C. and dilutedwith xylene to a 25% xylene solution. This solution has a barium sulfateash content of 41% and a reflux base number of 137.

EXAMPLE 19

A mixture of alkylated benzene sulfonic acids and naphtha is prepared byadding 1,000 parts of a mineral oil solution of the acid containing 18%by weight mineral oil (1.44 equivalents of acid) and 222 parts ofnaphtha. While stirring the mixture, 3 parts of calcium chloridedissolved in 90 parts of water and 53 parts of Mississippi lime (calciumhydroxide) is added. This mixture is heated to 97°-99° C. and held atthis temperature for 0.5 hour. Then 80 parts of Mississippi lime areadded to the reaction mixture with stirring and nitrogen gas is bubbledtherethrough to remove water, while heating to 150° C. over a three-hourperiod. The reaction mixture is then cooled to 50° C. and 170 parts ofmethanol are added. The resulting mixture is blown with carbon dioxideat a rate of two cubic feet per hour until substantially neutral. Thecarbon dioxide blowing is discontinued and the water and methanol arestripped from the reaction mixture by heating and bubbling nitrogen gastherethrough. While heating to remove the water and methanol, thetemperature rose to 146° C. over a 1.75-hour period. At this point themetal ratio of the overbased material is 2.5 and the product is a clear,dark-brown viscous liquid. This material is permitted to cool to 50° C.and thereafter 1,256 parts thereof are mixed with 574 parts of naphtha,222 parts of methanol, 496 parts of Mississippi lime, and 111 parts ofan equal molar mixture of isobutanol and amyl alcohol. The mixture isthoroughly stirred and carbon dioxide is blown therethrough at the rateof two cubic feet per hour for 0.5 hour. An additional 124 parts ofMississippi lime are added to the mixture with stirring and the CO.sub.2 blowing continued. Two additional 124-part increments of Mississippilime are added to the reaction mixture while continuing the carbonation.Upon the addition of the last increment, carbon dioxide is bubbledthrough the mixture for an additional hour. Thereafter, the reactionmixture is gradually heated to about 146° C. over a 3.25-hour periodwhile blowing the nitrogen to remove water and methanol from themixture. Thereafter, the mixture is permitted to cool to roomtemperature and filtered producing 1,895 parts of the desired overbasedmaterial having a metal ratio of 11.3. The material contains 6.8%mineral oil, 4.18% of the isobutanol-amyl alcohol and 30.1% naphtha.

EXAMPLE 20

1274 parts of methanol, 11.3 parts of calcium chloride and 90.6 parts oftap water are added to a resin reactor equipped with a heating mantle,thermocouple, gas inlet tube, condenser and metal stirrer. The mixtureis heated to 48° C. with stirring. 257.8 parts of Silo lime (calciumhydroxide) are added to provide a slurry. 2,830 parts of alkylatedbenzene sulfonic acid are added to the whole over a period of one hour.The temperature of the whole rises to 53° C. 2,510 parts of SC Solvent100 (a high-boiling alkylated aromatic solvent supplied by OhioSolvents) are added. The whole is stirred for 0.5 hour. Three incrementsof 709.1 parts each of Silo lime are added to the whole and carbondioxide at a rate of five cubic feet per hour is bubbled through thewhole after each increment. Total blowing with carbon dioxide isapproximately seven hours with the temperature of the whole varying from40° to 55° C. The reactor is equipped with a trap. Methanol and waterare stripped from the whole by bubbling nitrogen at a rate of two cubicfeet per hour through the whole over a 12-hour period while maintainingthe temperature of the whole at 155° C. The whole is held at atemperature of 155° C. for 15 minutes, and then cooled to roomtemperature. The whole is filtered through a Gyro Tester clarifier. Thesolids content is adjusted to 70% solids with SC Solvent 100.

EXAMPLE 21

A mixture of 406 parts of naphtha and 214 parts of amyl alcohol isplaced in a three-liter flask equipped with reflux condenser, gas inlettubes, and stirrer. The mixture is stirred rapidly while heating to 38°C. and adding 27 parts of barium oxide. Then 27 parts of water are addedslowly and the temperature rises to 45° C. Stirring is maintained whileadding 73 parts of oleic acid over a 0.25-hour period. The mixture isheated to 95° C. with continued mixing. Heating is discontinued and 523parts of barium oxide are slowly added to the mixture. The temperaturerises to about 115° C. and the mixture is permitted to cool to 90° C.whereupon 67 parts of water are slowly added to the mixture and thetemperature rises to 107° C. The mixture is then heated within the rangeof 107°-120° C. to remove water over a 3.3-hour period while bubblingnitrogen through the mass. Subsequently, 427 parts of oleic acid areadded over a 1.3-hour period while maintaining a temperature of120°-125° C. Thereafter heating is terminated and 236 parts of naphthaare added. Carbonation is commenced by bubbling carbon dioxide throughthe mass at two cubic feet per hour for 1.5 hours during which thetemperature is held at 108°-117° C. The mixture is heated under anitrogen purge to remove water. The reaction mixture is filtered twiceproducing a filtrate analyzing as follows: sulfate ash content, 34.42%;metal ratio, 313. The filtrate contains 10.7% amyl alcohol and 32%naphtha.

EXAMPLE 22

A reaction mixture of 1,800 parts of a calcium overbased petrosulfonicacid containing 21.7% mineral oil and 36.14% naphtha, 426 parts naphtha,255 parts of methanol, and 127 parts of an equal molar mixture ofisobutanol and amyl alcohol are heated to 45° C. under reflux conditionsand 148 parts of Mississippi lime (commercial calcium hydroxide) areadded thereto. The reaction mass is then blown with carbon dioxide at arate of two cubic feet per hour and thereafter 148 parts of additionalMississippi lime are added. Carbonation is continued for another hour atthe same rate. Two additional 147-part increments of Mississippi limeare added to the reaction mixture, each increment followed by about aone-hour carbonation process. Thereafter, the reaction mass is heated toa temperature of 138° C. while bubbling nitrogen therethrough to removewater and methanol. After filtration, 2,220 parts of a solution of thedispersed barium overbased petrosulfonate acid is obtained having ametal ratio of 12.2 and containing 12.5% mineral oil, 34.15% naphtha,and 4.03% of the isobutanol-amyl alcohol mixture.

EXAMPLE 23

A mixture of 1000 parts of a 60% mineral oil solution of sodiumpetroleum sulfonate (having a sulfated ash content of about 8.5%) and asolution of 71.3 parts of 96% calcium chloride in 84 parts of water ismixed at 100° C. for 0.25 hour. Then 67 parts of hydrated lime is addedand the whole is heated at 100° C. for 0.25 hour then dried by heatingto 145° C. to remove water. The residue is cooled and adjusted to 0.7%water content. 130 parts methanol are added and the whole is blown withcarbon dioxide at 45°-50° C. until it is substantially neutral. Waterand alcohol are removed by heating the mass to 150° C. and the resultingoil solution is filtered. The resulting product is carbonated calciumsulfonate overbased material containing 4.78% calcium and a metal ratioof 2.5.

A mixture of 1000 parts of the above carbonated calcium sulfonateoverbased material, 316 parts of mineral oil, 176 parts of methanol, 58parts of isobutyl alcohol, 30 parts of primary amyl alcohol and 52.6parts of the calcium phenate of Example 8 is prepared, heated to 35° C.,and subjected to the following operating cycle four times: mixing with93.6 parts of 97.3% calcium hydroxide and treating the mixture withcarbon dioxide until it has a base number of 35-45. The resultingproduct is heated to 150° C. and simultaneously blown with nitrogen toremove alcohol and water, and then filtered. The filtrate has a calciumcontent of 12.0% and a metal ratio of 12.

Examples 1-23 illustrate various means for preparing overbased materialssuitable for use in conversion to the non-Newtonian colloidal dispersesystems utilized in the present invention. Obviously, it is within theskill of the art to vary these examples to produce any desired overbasedmaterial. Thus, other acidic materials such as mentioned herebefore canbe substituted for the acidic materials used in the above examples.Similarly, other metal bases can be employed in lieu of the metal baseused in any given example, or mixtures of bases and/or mixtures ofmaterials which can be overbased can be utilized. Similarly, the amountof mineral oil or other non-polar, inert, organic liquid used as theoverbasing medium can be varied widely both during overbasing and in theoverbased product.

Examples 24-66 illustrate the conversion of Newtonian overbasedmaterials into non-Newtonian colloidal disperse systems byhomogenization with conversion agents.

EXAMPLE 24

To 733 parts of the overbased material of Example 4(a), there is added179 parts of acetic acid and 275 parts of a mineral oil (having aviscosity of 2000 SUS at 1000° F.) at 90° C. over a period of 1.5 hourswith vigorous agitation. The mixture is then homogenized at 150° C. fortwo hours and the resulting material is the desired colloidal dispersesystem.

EXAMPLE 25

A mixture of 960 parts of the overbased material of Example 4(b), 256parts of acetic acid, and 200 parts of a mineral oil (having a viscosityof 2000 SUS at 100° C.) is homogenized by vigorous stirring at 150° C.for two hours. The resulting product is a non-Newtonian colloidaldisperse system of the type contemplated for use by the presentinvention.

The overbased material of Examples 24 and 25 can be converted withoutthe addition of additional mineral oil or if another inert organicliquid is substituted for the mineral oil.

EXAMPLE 26

A mixture of 150 parts of the overbased material of Example 5, 15 partsof methyl alcohol, 10.5 parts of amyl alcohol, and 45 parts of water isheated under reflux conditions at 71°-74° C. for 13 hours whereupon themixture gels. The gel is heated for six hours at 144° C., diluted with126 parts of the mineral oil. The diluted mixture is heated to 144° C.for an additional 4.5 hours. The resulting thickened product is acolloidal disperse system. Again, it is not necessary that the materialbe diluted with mineral oil in order to be useful.

EXAMPLE 27

A mixture of 1000 parts of the product of Example 9, 80 parts ofmethanol, 40 parts of mixed primary amyl alcohols (containing about 65%normal amyl alcohol, 3% isoamyl alcohol, and 32% of 2-methyl-1-butylalcohol) and 80 parts of water are added to a reaction vessel and heatedto 70° C. and maintained at that temperature for 4.2 hours. Theoverbased material is converted to a gelatinous mass, the latter isstirred and heated at 150° C. for a period of about two hours to removesubstantially all the alcohols and water. The residue is a dark-greengel.

EXAMPLE 28

The procedure of Example 27 is repeated except that 120 parts of wateris used to replace the water-alkanol mixture employed as the conversionagent therein. Conversion of the Newtonian overbased material into thenon-Newtonian colloidal disperse system requires about five hours ofhomogenization. The disperse system is in the form of a gel.

EXAMPLE 29

To 600 parts of the overbased material of Example 5, there is added 300parts of dioctylphthalate, 48 parts of methanol, 36 parts of isopropylalcohol, and 36 parts of watar. The mixture is heated to 70°-77° C. andmaintained at this temperature for four hours during which the mixturebecomes more viscous. The viscous solution is then blown with carbondioxide for one hour until substantially neutral to phenylphthalein. Thealcohols and water are removed by heating to approximately 150° C. Theresidue is the desired colloidal disperse system.

EXAMPLE 30

To 800 parts of the overbased material of Example 5, there is added 300parts of kerosene, 120 parts of an alcohol-water mixture comprising 64parts of methanol, 32 parts of water and 32 parts of primary amylalcohol. The mixture is heated to 75° C. and maintained at thistemperature for two hours during which time the viscosity of the mixtureincreases. The water and alcohols are removed by heating the mixture toabout 150° C. while blowing with nitrogen for one hour. The residue isthe desired colloidal disperse system having the consistency of a gel.

EXAMPLE 31

A mixture of 340 parts of the product of Example 5, 68 parts of analcohol-water solution (the alcohol-water solution consisting of 27.2parts of methanol, 20.4 parts of isopropyl alcohol and 20.4 parts ofwater), and 170 parts of heptane is heated to 65° C. During this period,the viscosity of the mixture increases from an initial value of 6,250 to54,000.

The thickened colloidal disperse system is further neutralized byblowing the carbon dioxide at the rate of five pounds per hour for onehour. The resulting mass has a neutralization number of 0.87 (acid tophenolphthalein indicator).

EXAMPLE 32

The procedure of Example 31 is repeated except that the calciumoverbased material of Example 5 is replaced by an equivalent amount ofthe cadmium and barium overbased material of Example 12. Xylene (200parts) is used in lieu of the heptane and the further carbonation stepis omitted.

EXAMPLE 33

A mixture of 500 parts of the overbased material of Example 5, 312 partsof kerosene, 40 parts of methylethyl ketone, 20 parts of isopropylalcohol, and 50 parts of water is prepared and heated to 75° C. Themixture is maintained at a temperature of 70°-75° C. for five hours andthen heated to 150° C. to remove the volatile components. The mixture isthereafter blown with ammonia for 30 minutes to remove most of the finaltraces of volatile materials and thereafter permitted to cool to roomtemperature. The residue is a brownish-tan colloidal disperse system inthe form of a gel.

EXAMPLE 34

A mixture of 500 parts of the product of Example 5, 312 parts ofkerosene, 40 parts of acetone, and 60 parts of water is heated to refluxand maintained at this temperature for five hours with stirring. Thetemperature of the material is then raised to about 155° C. whileremoving the volatile components. The residue is a viscous gel-likematerial which is the desired colloidal disperse system.

EXAMPLE 35

The procedure of Example 34 is repeated with the substitution of 312parts of heptane for the kerosene and 60 parts of water for theacetone-water mixture therein. At the completion of the homogenization,hydrogen gas is bubbled through the gel to facilitate the removal ofwater and any other volatile components.

EXAMPLE 36

To 500 parts of the overhead material of Example 8, there is added 312parts of kerosene, 40 parts of o-cresol, and 50 parts of water. Thismixture is heated to the reflux temperature (70°-75° C.) and maintainedat this temperature for five hours. The volatile components are thenremoved from the mixture by heating to 150° C. over a period of twohours. The residue is the desired colloidal disperse system containingabout 16% by weight of kerosene.

EXAMPLE 17

A mixture of 500 parts of the overbased material of Example 4(a) and 312parts of heptane is heated to 80° C. whereupon 149 parts of glacialacetic acid (99.8%) is added dropwise over a period of five hours. Themixture is then heated to 150° C. to remove the volatile components. Theresulting gel-like material is the desired colloidal disperse system.

EXAMPLE 38

The procedure of Example 37 is repeated except that 232 parts of boricacid is used in lieu of the acetic acid. The desired gel is produced.

EXAMPLE 39

The procedure of Example 35 is repeated except that the water isreplaced by 40 parts of methanol and 40 parts of diethylene triamine.Upon completion of the homogenization, a gel-like colloidal dispersesystem is produced.

EXAMPLE 40

A mixture of 500 parts of the product of Example 5 and 300 parts ofheptane is heated to 80° C. and 68 parts of anthranilic acid is addedover a period of one hour while maintaining the reaction temperaturebetween 80° and 95° C. The reaction mixture is then heated to 150° C.over a two-hour period and then blown with nitrogen for 15 minutes toremove the volatile components. The resulting colloidal disperse systemis a moderately stiff gel.

EXAMPLE 41

The procedure of Example 40 is repeated except that the anthranilic acidis replaced by 87 parts of adipic acid. The resulting product is veryviscous and is the desired colloidal disperse system. This gel can bediluted, if desired, with mineral oil or any of the other materials saidto be suitable for disperse mediums hereinabove.

EXAMPLE 42

A mixture of 500 parts of the product of Example 7 and 300 parts ofheptane is heated to 80° C. whereupon 148 parts of glacial acetic acidis added over a period of one hour while maintaining the temperaturewithin the range of about 80°-88° C. The mixture is then heated to 150°C. to remove the volatile components. The residue is a viscous gel. Thisgel may be diluted with a material suitable as a disperse medium.

EXAMPLE 43

A mixture of 300 parts of toluene and 500 parts of an overhead materialprepared according to the procedure of Example 6 and having a sulfateash content of 41.8% is heated to 80° C. whereupon 124 parts of glacialacetic acid is added over a period of one hour. The mixture is thenheated to 175° C. to remove the volatile components. During thisheating, the reaction mixture becomes very viscous and 380 parts ofmineral oil is added to facilitate the removal of the volatilecomponents. The resulting colloidal disperse system is a viscousgrease-like material.

EXAMPLE 44

A mixture of 700 parts of the overbased material of Example 4(b), 70parts of water, and 350 parts of toluene is heated to reflux and blownwith carbon dioxide at the rate of one cubic foot per hour for one hour.The reaction product is a soft gel.

EXAMPLE 45

The procedure of Example 41 is repeated except that the adipic acid isreplaced by 450 parts of di(4-methyl-amyl)phosphorodithioic acid. Theresulting product is a gel.

EXAMPLE 46

The procedure of Example 39 is repeated except that the methanol-aminemixture is replaced by 250 parts of a phosphorus acid. The product is aviscous brown gel-like colloidal disperse system. The phosphorus acid isobtained by treating with steam at 150° C. the product obtained byreacting 1000 parts of polyisobutene having a molecular weight of about60,000, with 24 parts of phosphorus pentasulfide.

EXAMPLE 47

The procedure of Example 43 is repeated except that the overbasedmaterial therein is replaced by an equivalent amount of the potassiumoverbased material of Example 13 and the heptane is replaced by anequivalent amount of toluene.

EXAMPLE 48

The overbased material of Example 5 is isolated as a dry powder byprecipitation out of a benzene solution through the addition thereto ofacetone. The precipitate is washed with acetone and dried. A mixture of45 parts of a toluene solution of the above powder (364 parts of tolueneadded to 500 parts of the powder to produce a solution having a sulfateash content of 43%), 36 parts of methanol, 27 parts of water, and 18parts of mixed primary amyl alcohols (described in Example 27) is heatedto a temperature within the range of 70°-75° C. The mixture ismaintained at this temperature for 2.5 hours and then heated to removethe alkanols. The resulting material is a colloidal disperse systemsubstantially free from any mineral oil. If desired, the toluene presentin the colloidal disperse system as the disperse medium can be removedby first diluting the disperse system with mineral oil and thereafterheating the diluted mixture to a temperature of about 160° C. whereuponthe toluene is vaporized.

EXAMPLE 49

Calcium overbased material similar to that prepared in Example 5 is madeby substituting xylene for the mineral oil used therein. The resultingoverbased material has a xylene content of about 25% and a sulfate ashcontent of 39.3%. This overbased material is converted to a colloidaldisperse system by homogenizing 100 parts of the overbased material with8 parts of methanol, 4 parts of the amyl alcohol mixture of Example 27,and 6 parts of water. The reaction mass is mixed for six hours whilemaintaining the temperature at 75°-78° C. Thereafter, the dispersesystem is heated to remove the alkanols and water. If desired, the gelcan be diluted by the addition of mineral oil, toluene, xylene, or anyother suitable disperse medium.

EXAMPLE 50

A solution of 1000 parts of the gel-like colloidal disperse system ofExample 26 is dissolved in 1000 parts of toluene by continuous agitationof these two components for about three hours. A mixture of 1000 partsof the resulting solution, 20 parts of water, and 20 parts of methanolare added to a three-liter flask. Thereafter, 92.5 parts of calciumhydroxide is slowly added to the flask with stirring. An exothermicreaction takes place raising the temperature to 32° C. The entirereaction mass is then heated to about 60° C. over a 0.25-hour period.The heated mass is then blown with carbon dioxide at the rate of threestandard cubic feet per hour for one hour while maintaining thetemperature at 60°-70° C. At the conclusion of the carbonation, the massis heated to about 150° C. over a 0.75-hour period to remove water,methanol and toluene. The resulting product is a clear, light-browncolloidal disperse system in the form of a gel. In this manneradditional metal-containing particles are incorporated into thecolloidal disperse system.

At the conclusion of the carbonation step and prior to removing thewater, methanol and toluene, more calcium hydroxide could have beenadded to the mixture and the carbonation step repeated in order to addstill additional metal-containing particles to the colloidal dispersesystem.

EXAMPLE 51

A mixture of 1200 parts of the gel produced according to Example 26, 600parts of toluene, and 48 parts of water is blown with carbon dioxide attwo standard cubic feet per hour while maintaning the temperature at55°-65° C. for one hour. The carbonated reaction mass is then heated at150° C. for 1.75 hours to remove the water and toluene. This procedureimproves the texture of the colloidal disperse systems and converts anycalcium oxide or calcium hydroxide present in the gel into calciumcarbonate particles.

EXAMPLE 52

A mixture comprising 300 parts of water, 70 parts of the amyl alcoholmixture identified in Example 27 above, 100 parts of methanol, and 1000parts of a barium overbased oleic acid prepared according to the generaltechnique of Example 3 by substituting oleic acid for the petrosulfonicacid used therein and having a metal ratio of about 3.5, is thoroughlymixed for about 2.5 hours while maintaining the temperature within therange of from about 72°-74° C. At this point the resulting colloidaldisperse system is in the form of a very soft gel. This material is thenheated to about 150° C. for a two-hour period to expel methanol, theamyl alcohols, and water. Upon removal of these liquids, the colloidaldisperse system is a moderately stiff, gel-like material.

EXAMPLE 53

A dark brown colloidal disperse system in the form of a very stiff gelis prepared from the product of Example 19 using a mixture of 64 partsof methanol and 80 parts of water as the conversion agent to convert 800parts of the overbased material. After the conversion process, theresulting disperse system is heated to about 150° C. to remove thealcohol and water.

EXAMPLE 54

5000 parts of the product of Example 20 are placed in a resin reactorequipped with a heating mantle, thermocouple, gas-inlet tube, condenserand metal stirrer, and heated to 40° C. with stirring. Carbon dioxide isbubbled through this product at the rate of one cubic foot per hour for2.4 hours, the temperature of the whole varying from 40° C. to 44° C.282.6 parts of isopropyl alcohol, 282.6 parts of methanol and 434.8parts of distilled water are added over a five-minute period. The wholeis heated to 78° C. and refluxed for 30 minutes. 667 parts of SC Solvent100 are added. The reactor is equipped with a trap. Isopropyl alcohol,methanol and water are stripped from the whole by bubbling nitrogen attwo cubic feet per hour through the whole over a period of five hourswhile maintaining the temperature at 160° C. The whole is dried to 0.05%by weight water content and then cooled to room temperature. The solidscontent is adjusted to 60% solids with SC Solvent 100.

EXAMPLE 55

1000 parts of the overbased material of Example 21 is converted to acolloidal disperse system by using as a conversion agent a mixture of100 parts of methanol and 300 parts of water. The mixture is stirred forseven hours at a temperature within the range of 72°-80° C. At theconclusion of the mixing, the resulting mass is heated gradually to atemperature of about 150° C. over a three-hour period to remove allvotatile liquid contained therein. Upon removal of all volatilesolvents, a tan powder is obtained. By thoroughly mixing this tan powderwith a suitable organic liquid such as naphtha, it is again transformedinto a colloidal disperse system.

EXAMPLE 56

A mixture of 1000 parts of the product of Example 22, 100 parts ofwater, 80 parts of methanol, and 300 parts of naphtha are mixed andheated to 72° C. under reflux conditions for about five hours. A lightbrown viscous liquid material is formed which is the desired colloidaldisperse system. This liquid is removed and consists of the colloidaldisperse system wherein about 11.8% of the disperse medium is mineraloil and 88% is naphtha.

Following the techniques of Example 26, additional overbased materialsas indicated below are converted to the corresponding colloidal dispersesystems.

    ______________________________________                                                    Overbased material of below                                                   examples converted to colloidal                                   Example No. disperse system                                                   ______________________________________                                        57          Example 11                                                        58          Example 14                                                        59          Example 15                                                        60          Example 16                                                        61          Example 17                                                        62          Example 18                                                        63          Example 19                                                        64          Example 21                                                        ______________________________________                                    

EXAMPLE 65

A mixture of 1000 parts of the overbased material of Example 23 and388.4 parts of mineral oil is heated to 55°-60° C. and blown with carbondioxide until the base number is about one. 56.5 parts methanol and 43.5parts water are added and the whole is mixed at 75°-80° C. under refluxuntil the viscosity increases to a maximum. The maximum viscosity can bedetermined by visual inspection. 472.5 parts of 97.3% calcium hydroxideand 675.4 parts of mineral oil are added and the whole is blown withcarbon dioxide at a temperature of 75°-80° C. until the whole issubstantially neutral. Alcohol and water are removed by blowing thewhole with nitrogen at 150° C. The resulting product has a calciumcontent of 13.75% and a metal ratio of 36.

EXAMPLE 66

A first mixture of 57 parts methanol and 43 parts water is prepared. Asecond mixture is prepared by adding 220 parts N-heptane to 1000 partsof the product of Example 9. The second mixture is carbonated by blowingcarbon dioxide at 49°-55° C. to reduce the direct base number to 7-15.The first mixture of methanol and water is added to the carbonatedsecond mixture and mixed under reflux conditions at 62°-66° C. until agel is formed. This material is then heated to 149° C. andflash-stripped of N-heptane, alcohols and water over into mineral oil.This material is further dried by nitrogen blowing at 149°-160° C.Mineral oil is added to provide a No. 1 grease penetrationspecification.

The change in rheological properties associated with conversion of aNewtonian overbased material into a non-Newtonian colloidal dispersesystem is demonstrated by the Brookfield Viscometer data derived fromoverbased materials and colloidal disperse systems prepared therefrom.In the following samples, the overbased material and the colloidaldisperse systems are prepared according to the above-discussed andexemplified techniques. In each case, after preparation of the overbasedmaterial and the colloidal disperse system, each is blended withdioctylphthalate (DOP) so that the compositions tested in the viscometercontain 33.3% by weight DOP (Samples A, B and C) or 50% by weight DOP(Sample D). In Samples A-C, the acidic material used in preparing theoverbased material is carbon dioxide while in Sample D, acetic acid isused. The samples each are identified by two numbers, (1) and (2). Thefirst is the overbased material-DOP composition and the second thecolloidal disperse system-DOP composition. The overbased materials ofthe samples are further characterized as follows:

SAMPLE A

Calcium overbased petrosulfonic acid having a metal ratio of about 12.2.

SAMPLE B

Barium overbased oleic acid having a metal ratio of about 3.5.

SAMPLE C

Barium overbased petrosulfonic acid having a metal ratio of about 2.5.

SAMPLE D

Calcium overbased commercial higher fatty acid mixture having a metalratio of about 5.

The Brookfield Viscometer data for these compositions is tabulatedbelow. The data of all samples is collected at 25° C.

    ______________________________________                                        BROOKFIELD VISCOMETER DATA                                                    (Centipoises)                                                                 Sample A     Sample B  Sample C   Sample D                                    R.p.m. (1)    (2)    (1)  (2)  (1)  (2)   (1)  (2)                            ______________________________________                                         6     230    2,620  80   15,240                                                                             240   11,320                                                                             114  8,820                          12     235    2,053  90    8,530                                                                             230  6,980 103  5,220                          30     239    (.sup.1)                                                                             88   (.sup.1)                                                                           224  4,008 100  2,892                          ______________________________________                                         .sup.1 Off scale.                                                        

The Metal-Containing Organic Phosphate Complex (C)

The metal-containing organic phosphate complex (C) is prepared by theprocess which comprises the reaction of (C)(1) at least one polyvalentmetal salt of an acid phosphate ester derived from the reaction ofphosphorus pentoxide or phosphoric acid with a mixture of a monohydricalcohol and from about 0.25 to about four equivalents of a polyhydricalcohol with (C)(2) at least about 0.1 equivalent of an organic epoxide.The preparation of these phosphate complexes is described in U.S. Pat.No. 3,215,716, which is incorporated herein by reference.

The acid phosphate esters required for the preparation of startingmaterial (C)(1) are made, as indicated, by the reaction of phosphoruspentoxide or phosphoric acid with a mixture of a monohydric alcohol anda polyhydric alcohol. The precise nature of this reaction is notentirely clear, but it is known that a mixture of phosphate esters isformed. This mixture consists principally of acid phosphate esters,i.e., compounds of the general formula:

    (RO).sub.x PO(OH).sub.3-x

where x equals 1 or 2 and R is an organic group, although some neutraltriesters of the formula (RO)₃ PO may also be formed.

The nature and the stoichiometry of the reaction are complicated furtherby the fact that one of the reactants is a polyhydric alcohol. It ispossible, therefore, that the polyhydric alcohol forms cyclic and/orpolymeric phosphate esters when it reacts with phosphorus pentoxide.

The acid phosphate esters resulting from the reaction of one mole orphosphorus pentoxide with from about 2 to about 6 equivalents of amixture of monohydric and polyhydric alcohols are useful in thepreparation of starting material (C)(1). The term "equivalent" as usedherein reflects the hydroxyl equivalency of the alcohol. Thus, forexample, 1 mole of octyl alcohol is 1 equivalent thereof, 1 mole ofethylene glycol is 2 equivalents thereof, and 1 mole of glycerol is 3equivalents thereof.

Less than 2 or more than 6 equivalents of alcohol can be used, ifdesired, in the reaction with one mole of phosphorus pentoxide, althoughsuch amounts are not preferred for reasons of economy. When fewer than 2equivalents of alcohol are used, some unreacted phosphorus pentoxide mayremain in the product or precipitate therefrom. On the other hand, whensubstantially more than 6 equivalents of alcohol are used, unreactedalcohol would be present in the product. It is generally preferred toemploy from about 3 to about 5 equivalents of the alcohol mixture permole of phosphorus pentoxide or phosphoric acid.

The monohydric alcohols useful in the preparation of starting material(C)(1) are principally the non-benzenoid alcohols, i.e., the aliphaticand cycloaliphatic alcohols, although in some instances aromatic and/orheterocyclic substituents may be present. Thus, suitable monohydricalcohols include propyl, isopropyl, butyl, isobutyl, amyl, hexyl,cyclohexyl, heptyl, methylcyclohexyl, octyl, isooctyl, decyl, lauryl,tridecyl, oleyl, benzyl, beta-phenethyl, alpha-pyridylethyl, etc.,alcohols. Mixtures of such alcohols can also be used if desired.Substituents such as chloro, bromo, fluoro, nitro, nitroso, ester,ether, sulfide, keto, etc., which do not prevent the desired reactionmay also be present in the alcohol. In most instances, however, themonohydric alcohol will be an unsubstituted alkanol.

The polyhydric alcohols useful in the preparation of starting material(C)(1) are principally glycols, i.e., dihydric alcohols, althoughtrihydric, tetrahydric, and higher polyhydric alcohols may also be used.In certain instances, they may contain aromatic and/or heterocyclicsubstituents as well as chloro, bromo, fluoro, nitro, nitroso, ether,ester, sulfide, keto, etc., substituents. Thus, suitable polyhydricalcohols include ethylene glycol, diethylene glycol, triethylene glycol,propylene glycol, dipropylene glycol, 1,3-butanediol, glycerol, glycerolmonooleate, mono-phenyl ether of glycerol, mono-benzyl ether ofglycerol, 1,3,5-hexanetriol, pentaerythritol, sorbitol dioctanoate,pentaerythritol dioleate, and the like. In lieu of a single polyhydricalcohol, mixtures of two or more of such alcohols may be employed.

As indicated, starting material (C)(1) is prepared from a mixture ofmonohydric and polyhydric alcohols. The mixture may contain a singlemonohydric and a single polyhydric alcohol, or a plurality of one orboth of such alcohols. Preferably, about 0.25 to about 4 equivalents ofpolyhydric alcohol per equivalent of monohydric alcohol are used.Mixtures of isooctyl alcohol and dipropylene glycol are satisfactory anda mixture in which these alcohols are present in about equivalentamounts can be used.

The reaction between the alcohol mixture and phosphorus pentoxide orphosphoric acid is exothermic and can be carried out conveniently at atemperature ranging from room temperature or below to a temperature justbeneath the decomposition point of the mixture. Generally, reactiontemperatures within the range of from about 40° C. to about 200° C. aremost satisfactory. The reaction time required varies according to thetemperature and to the hydroxyl activity of the alcohols. At the highertemperatures, as little as 5 to 10 minutes may be sufficient forcomplete reaction. On the other hand, at room temperature 12 or morehours may be required. Generally it is most convenient to heat thealcohol mixture with phosphorus pentoxide or phosphoric acid for 0.5 to8 hours at 60°-120° C. In any event, the reaction is carried out untilperiodic acid number determinations on the reaction mass indicate thatno more acid phosphate esters are being formed.

The acid phosphate esters useful in the process of this invention canalso be prepared by separately reacting phosphorus oxide or phosphoricacid with the monohydric and polyhydric alcohols and then mixing theesters so formed. As mentioned below, solvents may be used when thephosphate esters are viscous or otherwise difficult to handle.

To facilitate mixing and handling, the reaction may be conducted in thepresence of an inert solvent. Generally such solvent is a petroleumdistillate hydrocarbon, an aromatic hydrocarbon, an ether, or a lowerchlorinated alkane, although mixtures of any such solvents can be used.Typical solvents include, e.g., petroleum aromatic spirits boiling inthe range about 120°-200° C., benzene, xylene, toluene, mesitylene,ethylene dichloride, diisopropyl ether, etc. In most instances, thesolvent is allowed to remain in the acid phosphate esters and ultimatelythe metal-containing organic phosphate complex, where it serves as avehicle for the convenient application of films to metal surfaces.

The conversion of the acid phosphate esters to the polyvalent metal saltmay be carried out by any of the various known methods for thepreparation of salts of organic acids such as, e.g., reaction of theacid-esters with a polyvalent metal base such as a metal oxide,hydroxide, or carbonate. Other suitable methods include, e.g., reactionof the acid-esters with a finely divided polyvalent metal, or themetathesis of a monovalent metal salt of the acid-esters with a solublesalt of the polyvalent metal such as, e.g., a nitrate, chloride, oracetate thereof.

The polyvalent metal of starting material (C)(1) may be any light orheavy polyvalent metal such as, e.g., zinc, cadmium, lead, iron, cobalt,nickel, barium, calcium, strontium, magnesium, copper, bismuth, tin,chromium, or manganese. A preference is expressed for the polyvalentmetals of Group II of the Periodic Table and of these, zinc isparticularly preferred. A preferred starting material (C)(1) is the zincsalt of the acid phosphate esters formed by the reaction of a mixture ofequivalent amounts of isooctyl alcohol and dipropylene glycol withphosphorus pentoxide.

The formation of the metal-containing organic phosphate complex ofcomponent (C) involves, as indicated, a reaction between startingmaterial (C)(1), the polyvalent metal salt of certain acid phosphateesters, and starting material (C)(2), the organic epoxide.

The organic epoxides are compounds containing at least one ##STR6##linkage where x is zero or an integer of from 1 to about 12. Examples ofuseful organic epoxides include the various substituted andunsubstituted alkylene oxides containing at least two aliphatic carbonatoms, such as, e.g., ethylene oxide, 1,2-propylene oxide, 1,3-propyleneoxide, 1,2-butylene oxide, pentamethylene oxide, hexamethylene oxide,1,2-octylene oxide, cyclohexene oxide, methyl cyclohexene oxide,1,2,11,12-diepoxydodecane, styrene oxide, alpha-methyl styrene oxide,beta-propiolactone, methyl epoxycaprylate, ethyl epoxypalmitate, propylepoxymyristate, butyl epoxystearate. epoxidized soybean oil, and thelike. Of the various available organic epoxides, it is preferred to usethose which contain at least 12 carbon atoms. Especially preferred arethose epoxides which contain at least 12 carbon atoms and also acarboxylic ester group in the molecule. Thus, the commercially availableepoxidized carboxylic ester, butyl epoxy stearate, is a preferredstarting material (C)(2) for the purpose of this invention. If desired,the organic epoxide may also contain substituents such as, e.g., chloro,bromo, fluoro, nitro, nitroso, ether, sulfide, keto, etc., in themolecule.

The stoichiometry of the reaction of the polyvalent metal salt of theacid phosphate ester with the organic epoxide, to form themetal-containing organic phosphate complex of component (C) is notprecisely known. There are indications, however, that the reactioninvolves about one equivalent each of the polyvalent metal salt and theorganic epoxide (for this reaction, one equivalent of an epoxide is thesame as one mole thereof). This is not to say that complexes made fromone equivalent of the polyvalent metal salt and less than or more thanone equivalent of the organic epoxide are unsuited for the purpose ofthis invention. Complexes prepared using as little as 0.1 or 0.25equivalent or as much as 1.5 to 2 or more equivalents of the organicepoxide per equivalent of polyvalent metal salt are satisfactory for thepurpose of this invention.

The reaction between the organic epoxide and the polyvalent metal saltof the acid phosphate esters is only slightly exothermic, so in order toinsure complete reaction some heat is generally supplied to the reactionmass. The time and temperature for this reaction are not particularlycritical; satisfactory results may be obtained by maintaining the massfor 0.5-6 hours at a temperature within the range of from about 40° C.to about 150° C. Ordinarily, the product is clear and does not require afiltration. In some instances, however, it may be desirable to filterthe product, particularly when the polyvalent metal salt startingmaterial has not been purified.

The following Examples 67-78 are illustrative of specific modes ofpreparing component (C). All parts and percentages are by weight unlessotherwise indicated.

EXAMPLE 67

49 parts of dipropylene glycol (0.73 equivalent), 95 parts (0.73equivalent) of isooctyl alcohol, and 133 parts of aromatic petroleumspirits boiling in the range of 158°-176° C. are added to a reactionvessel. The whole is stirred at room temperature and 60 parts (0.42mole) of phosphorus pentoxide are added portionwise over a period ofabout 0.5 hour. The heat of reaction causes the temperature to rise toabout 80° C. After all of the phosphorus pentoxide has been added, thewhole is stirred for an additional 0.5 hour at 95° C. The resulting acidphosphate esters show an acid number of 91 with bromophenol blue as anindicator.

The mixture of acid phosphate esters is converted to the correspondingzinc salt by reacting it with 34.5 parts of zinc oxide for 2.5 hours at95° C. Thereafter 356 parts (one equivalent per equivalent of zinc salt)of butyl epoxystearate is added to the zinc salt of 88° C. over a periodof about one hour and the whole is stirred for four hours at 90° C.Filtration of the mass yields 684 parts of a zinc-containing organicphosphate complex having the following analysis: Percent phosphorus,3.55; percent zinc, 3.78; and specific gravity, 1.009.

EXAMPLE 68

A cadmium-containing organic phosphate complex is made in the manner setforth in Example 67, except that 54.5 parts of cadmium oxide is used inlieu of the specified amount of zinc oxide.

EXAMPLE 69

A lead-containing organic phosphate complex is made in the manner setforth in Example 67, except that 95 parts of lead monoxide are used inlieu of the specified amount of zinc oxide.

EXAMPLE 70

A barium-containing organic phosphate complex is made in the manner setforth in Example 67, except that 73 parts of barium hydroxide are usedin lieu of the specified amount of zinc oxide.

EXAMPLE 71

A tin-containing organic phosphate complex is made in the manner setforth in Example 67, except that 57 parts of stannic oxide are used inlieu of the specified amount of zinc oxide.

EXAMPLE 72

520 parts of isooctyl alcohol (4 equivalents), 268 parts of isopropyleneglycol (4 equivalents), and 1031 parts of toluene are added to areaction vessel. The whole is stirred and 243 parts (1.71 moles) ofphosphorus pentoxide are added portionwise over a period of two hours.The exothermic character of the reaction causes the temperature to risefrom room temperature to 60° C. To insure complete reaction, the wholeis stirred for an additional four hours at 60° C. The resulting 50%solution of the acid phosphate esters in toluene shows an acid number of88 with bromphenol blue as an indicator.

1000 parts of the toluene solution of acid phosphate esters of thepreceding paragraph are converted to the corresponding zinc salt byreaction with 83 parts of zinc oxide for 5.5 hours at 40°-45° C.Filtration yields a clear, light-yellow toluene solution of the zincsalt. 360 parts of this toluene solution (0.34 equivalent) is heatedwith 25 parts (0.34 quivalent) of beta-propiolactone for 5.5 hours at50°-60° C. to yield the desired zinc-containing organic phosphatecomplex as a 55% solution in toluene. It has the following analysis:4.26% phosphorus and 5.05% zinc.

EXAMPLE 73

A toluene solution of acid phosphate esters is made in the manner setforth in Example 72.

994 parts of the indicated toluene solution of acid phosphate esters isheated with 76 parts of calcium hydroxide for five hours at 45°-60° C.Filtration yields the calcium salt of the acid phosphate esters as a 51%solution in toluene.

325 parts (0.52 equivalent) of the toluene solution of the calcium saltis heated with 220 parts (0.52 equivalent) of 85% butyl epoxystearatefor five hours at 50°-60° C. to prepare the desired calcium-containingorganic phosphate complex as a 71% solution in toluene. It has thefollowing analysis: 2.34% phosphorus and 1.65% calcium.

EXAMPLE 74

A batch of acid phosphate esters is made in the manner set forth inExample 72, except that the amount of toluene solvent employed isreduced to 443 parts so as to yield a more concentrated (70%) solutionof the esters in toluene.

290 parts of this toluene solution are neutralized with a mixture of28.2 parts of zinc oxide and 11.2 parts of calcium hydroxide for threehours at 50°-70° C. Filtration of the mass yields a mixed zinc-calciumsalt of the acid phosphate esters as a 73% solution in toluene.

116.2 parts of the above mixed zinc-calcium salt (0.19 equivalent) and80.4 parts (0.19 equivalent) of 85% butyl epoxystearate are heated forsix hours at 50°-60° C. to prepare an 84% solution in toluene of acalcium and zinc-containing organic phosphate complex. It has thefollowing analysis: 2.69% phosphorus; 0.22% calcium; and 3.13% zinc.

EXAMPLE 75

A zinc-containing organic phosphate complex is made in the manner setforth in Example 67, except for the following differences: 58 parts of1,2-propylene oxide is used in lieu of the butyl epoxystearate and thereaction between the zinc salt of the acid phosphate esters and the1,2-propylene oxide is carried out at 30°-35° C., rather than 88°-90° C.

EXAMPLE 76

A zinc-containing organic phosphate complex is made in the manner setforth in Example 67, except that 136 parts (0.73 equivalent) of laurylalcohol and 39 parts (0.73 equivalent) of diethylene glycol are used inlieu of the specified amounts of isooctyl alcohol and dipropyleneglycol.

EXAMPLE 77

A zinc-containing organic phosphate complex is made in the manner setforth in Example 67, except that 185 parts (1.17 equivalents) ofn-decanol-1 and 7.9 parts (0.29 equivalent) of pentaerythritol are usedin lieu of the specified amounts of isooctyl alcohol and dipropyleneglycol.

EXAMPLE 78

A solution of 49 parts (0.73 equivalent) of dipropylene glycol, 95 parts(0.73 equivalent) of isoctyl alcohol and 133 parts of toluene isprepared, and 60 parts (0.423 mole) of phosphorus pentoxide are addedover a period of about 0.5 hour at a temperature of from about 50° C. toabout 90° C. After all of the phosphorus pentoxide is added, the mixtureis stirred for an additional five hours at about 90° C. The resultingacid phosphate ester mixture has an acid number of 75 with bromphenolblue as an indicator.

This mixture of acid phosphate esters is converted to the correspondingzinc salt by reaction with 34.5 parts of zinc oxide for one hour at 93°C. The water and toluene is removed by heating the mixture to 160°C./100 mm. in nine hours. Thereafter, 356 parts (1 equivalent perequivalent of zinc salt) of butyl epoxystearate is added to the zincsalt over a period of one hour at about 125° C. and the mixture is thenmaintained for four hours at about 95° C. The mixture is filtered andthe filtrate has the following analysis: 4.71% zinc; and a specificgravity of 1.0515.

The Alkali and Alkaline Earth Metal Organic Acid Salts (D)

The alkali and alkaline earth metal organic acids of this invention arepreferably those containing at least 12 aliphatic carbons although theacids may contain as few as 8 aliphatic carbon atoms if the acidmolecule includes an aromatic ring such as phenyl, naphthyl, etc.Representative organic acids suitable for preparing these materials arediscussed and identified in detail in U.S. Pat. Nos. 2,616,904 and2,777,874, which are incorporated herein by reference. Oil-solublecarboxylic and sulfonic acids are particularly suitable. Illustrative ofthe carboxylic acids are palmitic acid, stearic acid, myristic acid,oleic acid, linoleic acid, behenic acid, hexatriacontanoic acid,tetrapropylene-substituted glutaric acid, polyisobutene(M.W.-5000)-substituted succinic acid, polypropylene,(M.W.-10,000)-substituted succinic acid, octadecyl-substituted adipicacid, chlorostearic acid, 9-methylstearic acid, dichlorostearic acid,stearylbenzoic acid, eicosane-substituted naphthoic acid,dilauryl-decahydro-naphthalene carboxylic acid, didodecyl-tetralincarboxylic acid, dioctylcyclohexane carboxylic acid, mixtures of theseacids, their alkali and alkaline earth metal salts, and/or theiranhydrides. Of the oil-soluble sulfonic acids, the mono-, di-, andtrialiphatic hydrocarbon substituted aryl sulfonic acids and thepetroleum sulfonic acids (petrosulfonic acids) are particularlypreferred. Illustrative examples of suitable sulfonic acids includemahogany sulfonic acids, petrolatum sulfonic acids,monoeicosane-substituted naphthalene sulfonic acids dodecylbenzenesulfonic acids, didodecylbenzene sulfonic acids, dinonylbenzene sulfonicacids, cetylchlorobenzene sulfonic acids, dilauryl beta-naphthalenesulfonic acids, the sulfonic acid derived by the treatment ofpolyisobutene having a molecular weight of 1500 with chlorosulfonicacid, nitronaphthalenesulfonic acid, paraffin wax sulfonic acid,cetyl-cyclopentane sulfonic acid, lauryl-cyclohexanesulfonic acids,polyethylene (M.W.-750) sulfonic acids, etc. Normally the aliphaticgroups will be alkyl and/or alkenyl groups such that the total number ofaliphatic carbons is at least 12.

Within this preferred group of overbased carboxylic and sulfonic acids,the barium and calcium over based mono-, di-, and trialkylated benzeneand naphthalene (including hydrogenated forms thereof), petrosulfonicacids, and higher fatty acids are especially preferred. Illustrative ofthe synthetically produced alkylated benzene and naphthalene sulfonicacids are those containing alkyl substituents having from 8 to about 30carbon atoms therein. Such acids include di-isododecyl-benzene sulfonicacid, wax-substituted phenol sulfonic acid, wax-substituted benzenesulfonic acids, polybutene-substituted sulfonic acid, cetylchlorobenzenesulfonic acid, di-cetylnaphthalene sulfonic acid, di-lauryldiphenylethersulfonic acid, di-isononylbenzene sulfonic acid, di-isooctadecylbenzenesulfonic acid, stearylnaphthalene sulfonic acid, and the like. Thepetroleum sulfonic acids are particularly preferred. Petroleum sulfonicacids are obtained by treating refined or semi-refined petroleum oilswith concentrated or fuming sulfuric acid. These acids remain in the oilafter the settling out of sludges. These petroleum sulfonic acids,depending on the nature of the petroleum oils from which they areprepared, are oil-soluble alkane sulfonic acid, alkyl-substitutedcycloaliphatic sulfonic acids including cycloalkyl sulfonic acids andcycloalkene sulfonic acids, and alkyl, alkaryl, or aralkyl substitutedhydrocarbon aromatic sulfonic acids including single and condensedaromatic nuclei as well as partially hydrogenated forms thereof.Examples of such petrosulfonic acids include mahogany sulfonic acid,white oil sulfonic acid, petrolatum sulfonic acid, petroleum naphthenesulfonic acid, etc. This especially preferred group of aliphatic fattyacids includes the saturated and unsaturated higher fatty acidscontaining from 12 to 30 carbon atoms. Illustrative of these acids arelauric acid, palmitic acid, oleic acid, linoleic acid, linolenic acid,oleostearic acid, stearic acid, myristic acid, and undecalinic acid,alphachlorostearic acid, and alpha-nitrolauric acid.

The metal base can be an alkali or alkaline earth metal (e.g., sodium,potassium, calcium, barium, etc.) oxide, hydroxide, bicarbonate,sulfide, mercaptide, hydride, alcoholate or phenate. The acid salts areformed by mixing the metal base with the organic acid using mixingprocedures well known in the art.

The Carboxylic Acid (E)

The carboxylic acids of the present invention are one or more mono- orpolycarboxylic acids of one to about 20 carbon atoms such as fatty acidshaving 10 to about 18 carbon atoms.

Typical monocarboxylic acids include saturated and unsaturated fattyacids, such as lauric acid, stearic acid, oleic acid, myristic acid,linoleic acid, and the like. Anhydrides, when available, and lower alkylesters of these acids can also be used. Mixtures of two or more suchacids can also be used. An extensive discussion of such acids is foundin Kirk-Othmer "Encyclopedia of Chemical Technology" 2nd Edition, 1965,John Wiley & Sons, N.Y., pages 811-856. Acetic acid, propionic acid,butyric acid, acrylic and benzoic acid as well as their anhydrides andlower alkyl esters are also useful.

Among the useful polycarboxylic acids are maleic acid, fumaric acid,itaconic acid, mesaconic acid, succinic acid, phthalic acid,alkyl-substituted phthalic acids, isophthalic acid, malonic acid,glutaric acid, adipic acid, citraconic acid, glutaconic acid,chloromaleic acid, ataconic acid, scorbic acid, etc. Again anhydrideswhen available, and lower alkyl esters and esters of these acids can beused.

Certain lower molecular weight substituted succinic acids and anhydridescan also be used. A number of these are discussed in the above-citedKirk-Othmer article at pages 847-849. The typical such acylating agentscan be represented by the formula: ##STR7## wherein R* is a C₁ to abouta C₁₀ hydrocarbyl group. Preferably, R* is an aliphatic or alicyclichydrocarbyl group with less than 10% of its carbon-to-carbon bonds beingunsaturated. Examples of such groups are 4-butylcyclohexyl,di(isobutyl), decyl, etc. The production of such substituted succinicacids and their derivatives via alkylation of maleic acid or itsderivatives with a halohydrocarbon is well known to those of skill inthe art and need not be discussed in detail at this point.

The N-(Hydroxyl-Substituted Hydrocarbyl)Amines (F)

The N-(hydroxyl-substituted hydrocarbyl) amines (F) of the presentinvention generally have one to about four, typically one to about twohydroxyl groups per molecule. These hydroxyl groups are each bonded to ahydrocarbyl group to form a hydroxyl-substituted hydrocarbyl groupwhich, in turn, is bonded to the amine portion of the molecule. TheseN-(hydroxyl-substituted hydrocarbyl) amines can be monoamines orpolyamines and they can have a total of up to about 40 carbon atoms;generally they have a total of about 20 carbon atoms. Typically,however, they are monoamines containing but a single hydroxyl group.These amines can be primary, secondary or tertiary amines while theN-(hydroxyl-substituted hydrocarbyl) polyamines can have one or more ofany of these types of amino groups. Mixtures of two or more of any ofthe afore-described amines can also be used to make the component (F) ofthe invention.

Specific examples N-(hydroxyl-substituted hydrocarbyl)amines suitablefor use in this invention are the N-(hydroxy-lower alkyl)amines andpolyamines such as 2-hydroxyethylamine, 3-hydroxybutylamine,di-(2-hydroxyethyl)amine, tri-(2-hydroxyethyl)amine,di-(2-hydroxypropyl)amine, N,N,N'-tri-(2-hydroxyethyl)ethylenediamine,N,N,N',N'-tetra(2-hydroxyethyl)ethylenediamine,N-(2-hydroxyethyl)piperazine, N,N'-di-(3-hydroxypropyl)piperazine,N-(2-hydroxyethyl)morpholine, N-(2-hydroxyethyl)-2-morpholinone,N-(2-hydroxyethyl)-3-methyl-2-morpholinone,N-(2-hydroxypropyl)-6-methyl-2-morpholinone,N-(2-hydroxypropyl)-5-carbethoxy-2-piperidone,N-(2-hydroxypropyl)-5-carbethoxy-2-piperidone,N-(2-hydroxyethyl)-5-(N-butylcarbamyl)-2-piperidone,N-(2-hydroxyethyl)piperidine, N-(4-hydroxybutyl)piperidine,N,N-di-(2-hydroxyethyl)glycine, and ethers thereof with aliphaticalcohols, especially lower alkanols, N,N-di(3-hydroxypropyl)glycine, andthe like.

Further amino alcohols are the hydroxy-substituted primary aminesdescribed in U.S. Pat. No. 3,576,743 (which is incorporated herein byreference) by the formula

    R.sub.a --NH.sub.2

where R_(a) is a monovalent organic radical containing at least onealcoholic hydroxy group. According to this patent, the total number ofcarbon atoms in R_(a) will not exceed about 20. Hydroxy-substitutedaliphatic primary amines containing a total of up to about 10 carbonatoms are useful. Generally useful are the polyhydroxy-substitutedalkanol primary amines wherein there is only one amino group present(i.e., a primary amino group) having one alkyl substituent containing upto 10 carbon atoms and up to 4 hydroxyl groups. These alkanol primaryamines correspond to R_(a) NH₂ wherein R_(a) is a mono- orpolyhydroxy-substituted alkyl group. It is typical that at least one ofthe hydroxyl groups be a primary alcoholic hydroxyl group.Tris-methylolaminomethane is a typical hydroxy-substituted primaryamine. Specific examples of the hydroxy-substituted primary aminesinclude 2-amino-1-butanol, 2-amino-2-methyl-1-propanol,p-(betahydroxyethyl)-analine, 2-amino-1-propanol, 3-amino-1-propanol,2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol,N-(betahydroxypropyl)-N'-beta-aminoethyl)piperazine, 2-amino-1-butanol,ethanolamine, beta-(betahydroxy ethoxy)-ethyl amine, glucamine,glusoamine, 4-amino-3-hydroxy-3-methyl-1-butene (which can be preparedaccording to procedures known in the art by reacting isopreneoxide withammonia), N-3-(aminopropyl)-4(2-hydroxyethyl)piperadine,2-amino-6-methyl-6-heptanol, 5-amino-1-pentanol,N-(beta-hydroxyethyl)-1,3-diamino propane, 1,3-diamino-2-hydroxypropane,N-(beta-hydroxy ethoxyethyl)-ethylenediamine, and the like.

Typically, the amine (F) is a primary, secondary or tertiary alkanolamine or mixture thereof. Such amines can be represented, respectively,by the formulae: ##STR8## wherein each R is independently a hydrocarbylgroup of 1 to about 8 carbon atoms or hydroxy-substituted hydrocarbylgroup of 2 to about 8 carbon atoms and R' is a divalent hydrocarbylgroup of about 2 to about 18 carbon atoms. The group --R'--OH in suchformulae represents the hydroxyl-substituted hydrocarbyl group. R' canbe an acyclic, alicyclic or aromatic group. Typically, it is an acyclicstraight or branched alkylene group such as an ethylene, 1,2-propylene,1,2-butylene, 1,2-octadecylene, etc. group. Where two R groups arepresent in the same molecule they can be joined by a directcarbon-to-carbon bond or through a heteroatom (e.g., oxygen, nitrogen orsulfur) to form a 5-, 6-, 7- or 8-membered ring structure. Examples ofsuch heterocyclic amines include N-(hydroxyl lower alkyl)-morpholines,-thiomorpholines, -piperidines, -oxazolidines, -thiazolidines and thelike. Typically, however, each R is a lower alkyl group of up to 7carbon atoms.

The amine (F) can also be selected from the alkylene oxide condensates(i.e., alkoxylates) with active hydrogen compounds such as alcohols,phenols, amides and amines. The amides are often fatty acid amides suchas oleyl amides. A particularly useful class are the ethoxylated amineswherein the amine has at least 12 carbon atoms. Such amines can berepresented by the general formulae: ##STR9## and ##STR10## wherein R isan aliphatic hydrocarbyl group with at least about 12 carbon atoms, x, yand z are integers of zero to 40 and the sum of x+y is between 2 and 50.Usually the aliphatic group R has a maximum of about 22 carbons. Oftensuch R groups are fatty alkyl or alkenyl groups such as coco (C₁₂),stearyl (C₁₈), tallow (C₁₈), oleyl (C₁₈), and the like. Typically R is atallow residue and the sum x+y is about 5. Homologous alkoxylated amineswherein the ethoxyl residue (--CH₂ CH₂ O--) is replaced, at least inpart, by a propoxyl residue ##STR11## are also useful.

Mixtures of one or more of the afore-described amines can be used.

The compositions of the present invention contain an effective amount ofwater to provide a stable dispersion or emulsion (water-in-oil oroil-in-water) of the components of the compositions of the invention.Generally, the compositions of the invention have about 5% to about 99%preferably about 25% to about 75% by weight water. These compositionsgenerally contain from about 5% to about 70% by weight, preferably about40% to about 60%, and advantangeously about 50% to about 55% by weightof component (B). The weight ratio of component (B) to component (C) isgenerally from about 0.25:1 to about 10:1, preferably about 1:1 to about5:1. These compositions generally contain from about 15% to about 75% byweight, preferably about 15% to about 30% by weight of component (D).The level of component (E) is generally in the range of about 0.5% toabout 10% by weight, preferably about 1% to about 5%, and advantageouslyabout 2% to about 4%. The level of addition of component (F) isdependent upon the level of addition of component (E). It is preferableto provide a stoichiometric excess of component (F) over component (E)so as to neutralize component (E) and provide the compositions of thepresent invention with a slightly alkaline character. Generally thesecompositions have a pH ranging from slightly alkaline to about 10,preferably from about 8 to about 9.

The compositions of the present invention include aqueous concentrateswhich contain an effective amount of water to reduce the viscosity ofsuch compositions to facilitate shipping and handling. Generally, theseaqueous concentrates contain at least about 25% by weight water,preferably about 25% to about 75% water, and advantageously about 60% toabout 75% water. The aqueous concentrates of the invention can often beused as such without additional water depending upon the desired enduse. Alternatively, these concentrates can be further diluted by theaddition of water using standard mixing techniques if desired.

Generally, the corrosion-inhibiting coating compositions of the presentinvention contain about 60% to about 90%, preferably about 70% to about80% by weight water.

On the other hand, the compositions intended for use as metal-workingfluids require additional levels of water. These metal-working fluidsgenerally require about 80% to about 99%, preferably about 90% to about97% by weight water.

As indicated above, the compositions of the invention also includeaqueous drilling fluids. These drilling fluids contain a major amount ofan aqueous drilling mud and a minor torque reducing amount of components(B) and (C). Preferably these drilling fluids also contain an effectiveamount of components (D), (E) and (F) to disperse components (B) and (C)in the drilling mud. The relative ratios of components (B), (C), (D),(E) and (F) are within the ratios set forth above. The drilling fluidsof the invention generally contain about 90% to about 99.5% by weight ofan aqueous drilling mud. Components (B), (C), (D), (E) and (F) can beadded directly to the drilling mud or they may be first formulated as anaqueous concentrate, as discussed above and then added to the drillingmud. It is preferable to formulate these compositions in the form of anaqueous concentrate of the type discussed above for purposes offacilitating shipping and handling prior to addition to the drillingmud.

The drilling fluids of the present invention can also contain othermaterials which are known to be used in such applications, such as claythickeners, density-increasing agents such as barites, rust-inhibitingand corrosion-inhibiting agents, surfactants and acid or basic reagentsto adjust the pH of the drilling fluid. A typical drilling fluid withinthe scope of the present invention is made from a 5% by weight bentoniteclay slurry using well known techniques.

EXAMPLE 79

240 parts of oleic acid and 160 parts of triethanolamine are mixed fortwo minutes at room temperature. 1600 parts of sodium petroleumsulfonate dispersed in oil (61% by weight sodium petroleum sulfonate)and 1600 parts of the product of Example 67 are added and the whole isstirred for five minutes at room temperature. 4400 parts of the productof Example 66 are added to the whole over a period of one-half hourwhile heating to 65° C. The temperature of the whole is maintained at65° C. for an additional one-half hour. The whole is cooled to 49° C.while mixing over a period of one-half hour and then cooled to roomtemperature to provide the desired product which is in the form of apourable soft gel.

EXAMPLE 80

The product of Example 79 is dispersed with water at a temperature of60° C. to form a series of stable emulsions as indicated in Table Ibelow.

                  TABLE I                                                         ______________________________________                                        Product of                                                                    Example 79                                                                              Water         Type of                                               (Wt. %)   (Wt. %)       Emulsion  pH                                          ______________________________________                                         5        95             o/w*     8.16                                        10        90            o/w       8.0                                         15        85            o/w       8.02                                        20        80            o/w       8.22                                        25        75            o/w       8.0                                         30        70            o/w       8.12                                        40        60            Borderine 8.34                                        50        50             w/o**    7.24                                        75        25            w/o       7.33                                        ______________________________________                                         *o/w is an abbreviation for oilin-water.                                      **w/o is an abbreviation for waterin-oil.                                

EXAMPLE 81

240 parts of oleic acid and 160 parts of dimethyl ethanol amine aremixed for about two minutes at room temperature. 800 parts of the sodiumpetroleum sulfonate identified in Example 79 and 800 parts of theproduct of Example 67 are added and the whole is stirred for about fiveminutes at room temperature. 2000 parts of the product of Example 66 areadded to the whole over a period of about one-half hour while heating toabout 65° C. The temperature of the whole is maintained at 65° C. for anadditional one-half hour. The whole is cooled to about 49° C. whilemixing over a period of one-half hour, and then cooled to roomtemperature to provide the desired product.

EXAMPLE 82

The product of Example 81 is mixed with water having a temperature of2°-5° C. to provide stable emulsions at levels of 60%, 65%, 70%, 75%,80%, 90% and 95% by weight water.

EXAMPLE 83

240 parts of oleic acid and 160 parts of dimethyl ethanol amine aremixed for about two minutes at room temperature. 1200 parts of thesodium petroleum sulfonate identified in Example 79 and 1200 parts ofthe product of Example 67 are added, and the whole is stirred for aboutfive minutes at room temperature. 1200 parts of the product of Example66 are added to the whole over a period of about one-half hour whileheating to about 65° C. The temperature of the whole is maintained at65° C. for an additional one-half hour. The whole is cooled to about 49°C. while mixing, and then cooled to room temperature to provide thedesired product.

EXAMPLE 84

Stable emulsions are provided by mixing appropriate amounts of theproduct of Example 82 with water having a temperature of about 2°-5° C.to provide emulsions containing 60%, 65%, 70%, 75%, 80%, 90% and 95% byweight water.

While the invention has been explained in relation to its preferredembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications as fall withinthe scope of the appended claims.

I claim:
 1. A composition comprising:(A) water; (B) an overbasednon-Newtonian colloidal disperse system comprising (B)(1) solidmetal-containing colloidal particles predispersed in (B)(2) a dispersingmedium of at least one inert organic liquid and (B)(3) at least onemember selected from the class consisting of organic compounds which aresubstantially soluble in said dispersing medium, the molecules of saidorganic compound being characterized by polar substituents andhydrophobic portions; and (C) a metal-containing organic phosphatecomplex derived from the reaction of (C)(1) at least one polyvalentmetal salt of an acid phosphate ester, said acid phosphate ester beingderived from the reaction of phosphorus pentoxide or phosphoric acidwith a mixture of at least one monohydric alcohol and at least onepolyhydric alcohol, with (C)(2) at least one organic epoxide;components(B) and (C) being dispersed with said water.
 2. The composition of claim1 wherein said solid metal-containing colloidal particles (B)(1) arecharacterized by an average unit particle size of about 20 A. to about5000 A.
 3. The composition of claim 1 wherein said dispersing medium(B)(2) is a combination of mineral oil and at least one other organicliquid miscible with said mineral oil.
 4. The composition of claim 1wherein said solid-metal containing particles (B)(1) are selected fromthe group consisting of alkali and alkaline earth metal salts.
 5. Thecomposition of claim 1 wherein component (B)(3) comprises at least onemember selected from the group consisting of alkali and alkaline earthmetal salts of an oil-soluble organic acid.
 6. The composition of claim1 wherein said solid metal-containing colloidal particles (B)(1) areselected from the group consisting of alkaline earth metal acetates,formates, carbonates, hydrogen carbonates, hydrogen sulfides, sulfites,hydrogen sulfites, and chlorides.
 7. The composition of claim 1 whereinthe ratio of monohydric and polyhydric alcohols to phosphorus pentoxideor phosphoric acid in derivation of said acid phosphate ester is about 2to about 6 moles of said monohydric and polyhydric alcohols per mole ofsaid phosphorus pentoxide or phosphoric acid.
 8. The composition ofclaim 1 wherein the ratio of polyhydric alcohols to monohydric alcoholsin the derivation of said acid phosphate ester is about 0.25 to about 4equivalents polyhydric alcohol per equivalent of monohydric alcohol. 9.The composition of claim 1 wherein the metal of said polyvalent metalsalt (C)(1) is selected from the group consisting of zinc, cadmium,lead, iron, cobalt, nickel, barium, calcium, strontium, magnesium,copper, bismuth, tin, chromium and manganese.
 10. The composition ofclaim 1 wherein said organic epoxide (C)(2) contains at least onelinkage of the formula ##STR12## wherein x is zero or an integer of from1 to about
 12. 11. The composition of claim 1 wherein the ratio ofcomponents (C)(1) to (C)(2) is in the range of about 0.1 to about 2equivalents of (C)(2) per equivalent of (C)(1).
 12. The composition ofclaim 1 wherein the weight ratio of component (B) to component (C) isfrom about 0.25:1 to about 10:1.
 13. The composition of claim 1 with aneffective amount of (D) an alkali or alkaline earth metal salt of anorganic acid to enhance the dispersion of components (B) and (C) withsaid water (A).
 14. The composition of claim 1 with an effective amountof (E) a carboxylic acid to enhance the dispersion of components (B) and(C) with said water (A).
 15. The composition of claim 1 with aneffective amount of (F) an N-(hydroxyl-substituted hydrocarbyl)amine toenhance the dispersion of components (B) and (C) with said water (A).16. The composition of claim 1 with an effective amount of of (D) analkali or alkaline earth metal salt of an organic acid, (E) a carboxylicacid and (F) an N-(hydroxyl-substituted hydrocarbyl) amine to enhancethe dispersion of components (B) and (C) with said water (A).
 17. Thecomposition of claim 1 with an effective amount of a sodium petroleumsulfonate, oleic acid and triethanol amine to enhance the dispersion ofcomponents (B) and (C) with said water (A).
 18. The composition of claim1 with an effective amount of water (A) to disperse components (B) and(C) in said water.
 19. The composition of claim 1 wherein said water (A)is dispersed in components (B) and (C).
 20. The composition of claim 1wherein said composition comprises from about 5% to about 99% by weightwater.
 21. The composition of claim 1 wherein said composition comprisesfrom about 25% to about 75% by weight water.
 22. A method of inhibitingthe corrosion of a metal surface comprising coating said surface withthe composition of claim
 1. 23. A method of working metal comprisingcontacting said metal with the composition of claim 1.